Quaternized fatty amines, amidoamines and their derivatives from natural oil

ABSTRACT

Quaternary ammonium, betaine, or sulfobetaine compositions derived from fatty amines, wherein the fatty amine is made by reducing the amide reaction product of a metathesis-derived C 10 -C 17  monounsaturated acid, octadecene-1,18-dioic acid, or their ester derivatives and a secondary amine, are disclosed. Quaternary ammonium, betaine, or sulfobetaine compositions derived from fatty amidoamines, wherein the amidoamine is made by reacting of a metathesis-derived C 10 -C 17  monounsaturated acid, octadecene-1,18-dioic acid, or their ester derivatives and an aminoalkyl-substituted tertiary amine, are also disclosed. The quaternized compositions are advantageously sulfonated or sulfitated. In one aspect, the ester derivative of the C 10 -C 17  monounsaturated acid or octadecene-1,18-dioic acid is a lower alkyl ester. In other aspects, the ester derivative is a modified triglyceride N made by self-metathesis of a natural oil or an unsaturated triglyceride made by cross-metathesis of a natural oil with an olefin. The quaternary ammonium, betaine, and sulfobetaine compositions and their sulfonated or sulfitated derivatives are valuable for a wide variety of end uses, including cleaners, fabric treatment, hair conditioning, personal care (liquid cleansing products, conditioning bars, oral care products), antimicrobial compositions, agricultural uses, and oil field applications.

This application is a division of U.S. application Ser. No. 13/879,786,filed May 15, 2013, now allowed, which is a national stage filing under35 U.S.C. §371 of PCT/US2011/057605, filed Oct. 25, 2011, which claimsthe benefit of U.S. provisional applications 61/406,570, 61/406,556, and61/406,547, all filed Oct. 25, 2010.

FIELD OF THE INVENTION

The invention relates to quaternized fatty amines, amidoamines, andderivative compositions that originate from natural resources,particularly natural oils and their metathesis products.

BACKGROUND OF THE INVENTION

“Fatty amines” generally have a nonpolar chain of six or more carbons,typically 6-30 carbons, and at least one polar end group comprising orderived from an amine, for example, a tertiary amine. Fatty amines havevalue in and of themselves, but they are commonly quaternized using avariety of alkylating agents to give fatty amine quats, betaines,sulfobetaines, or other quaternized derivatives having expanded utility.

Quaternized fatty amines have been used in a wide range of end-useapplications, including fabric softening (see U.S. Pat. Nos. 5,574,179and 6,004,913), shampoos and hair conditioning (U.S. Pat. Nos.4,744,977, 6,322,778, and 7,951,762), hard surface cleaners (U.S. Pat.Nos. 6,268,324 and 6,821,943), cosmetics (U.S. Pat. Nos. 6,919,074 and7,074,395), oral care (U.S. Pat. No. 7,534,816), antimicrobial handsoapsor cleaners (U.S. Pat. No. 6,010,991 and U.S. Pat. Appl. Publ. No.2004/0071653), oilfield applications (U.S. Pat. Nos. 7,422,064 and7,776,798) and agricultural uses (U.S. Pat. Appl. Publ. Nos.2011/0015071 and 2010/0016163).

Quaternized fatty amines can be made by converting fatty esters or acidswith a secondary amine to the amide derivative, followed by reduction ofthe carbonyl to give a terminal tertiary amine, which is then reactedwith a quaternizing agent. In a preferred approach, the reduction stepis avoided by reacting a fatty ester with an aminoalkyl-substitutedtertiary amine. For instance, N,N-dimethyl-1,3-propanediamine (DMAPA)reacts with a fatty methyl ester to give a fatty amidoamine. Theamidoamine has a terminal tertiary amine group that is easilyquaternized. Common quaternizing agents are dimethyl sulfate, methylchloride, benzyl chloride, ethylene oxide, and the like.

The fatty acids or esters used to make fatty amines and theirderivatives are usually made by hydrolysis or transesterification oftriglycerides, which are typically animal or vegetable fats.Consequently, the fatty portion of the acid or ester will typically have6-22 carbons with a mixture of saturated and internally unsaturatedchains. Depending on source, the fatty acid or ester often has apreponderance of C₁₆ to C₂₂ component. For instance, methanolysis ofsoybean oil provides the saturated methyl esters of palmitic (C₁₆) andstearic (C₁₈) acids and the unsaturated methyl esters of oleic (C₁₈mono-unsaturated), linoleic (C₁₈ di-unsaturated), and α-linolenic (C₁₈tri-unsaturated) acids. The unsaturation in these acids has eitherexclusively or predominantly cis-configuration.

Recent improvements in metathesis catalysts (see J. C. Mol, Green Chem.4 (2002) 5) provide an opportunity to generate reduced chain length,monounsaturated feedstocks, which are valuable for making detergents andsurfactants, from C₁₆ to C₂₂-rich natural oils such as soybean oil orpalm oil. Soybean oil and palm oil can be more economical than, forexample, coconut oil, which is a traditional starting material formaking detergents. As Professor Mol explains, metathesis relies onconversion of olefins into new products by rupture and reformation ofcarbon-carbon double bonds mediated by transition metal carbenecomplexes. Self-metathesis of an unsaturated fatty ester can provide anequilibrium mixture of starting material, an internally unsaturatedhydrocarbon, and an unsaturated diester. For instance, methyl oleate(methyl cis-9-octadecenoate) is partially converted to 9-octadecene anddimethyl 9-octadecene-1,18-dioate, with both products consistingpredominantly of the trans-isomer. Metathesis effectively isomerizes thecis-double bond of methyl oleate to give an equilibrium mixture of cis-and trans-isomers in both the “unconverted” starting material and themetathesis products, with the trans-isomers predominating.

Cross-metathesis of unsaturated fatty esters with olefins generates newolefins and new unsaturated esters that can have reduced chain lengthand that may be difficult to make otherwise. For instance,cross-metathesis of methyl oleate and 3-hexene provides 3-dodecene andmethyl 9-dodecenoate (see also U.S. Pat. No. 4,545,941). Terminalolefins are particularly desirable synthetic targets, and ElevanceRenewable Sciences, Inc. recently described an improved way to preparethem by cross-metathesis of an internal olefin and an α-olefin in thepresence of a ruthenium alkylidene catalyst (see U.S. Pat. Appl. Publ.No. 2010/0145086). A variety of cross-metathesis reactions involving anα-olefin and an unsaturated fatty ester (as the internal olefin source)are described. Thus, for example, reaction of soybean oil with propylenefollowed by hydrolysis gives, among other things, 1-decene, 2-undecenes,9-decenoic acid, and 9-undecenoic acid. Despite the availability (fromcross-metathesis of natural oils and olefins) of unsaturated fattyesters having reduced chain length and/or predominantlytrans-configuration of the unsaturation, fatty amines and theirderivatives made from these feedstocks appear to be unknown. Moreover,quaternized fatty amines and their derivatives have not been made fromthe C₁₈ unsaturated diesters that can be made readily by self-metathesisof a natural oil.

In sum, traditional sources of fatty acids and esters used for makingquaternized fatty amines and their derivatives generally havepredominantly (or exclusively) cis-isomers and lack relativelyshort-chain (e.g., C₁₀ or C₁₂) unsaturated fatty portions. Metathesischemistry provides an opportunity to generate precursors having shorterchains and mostly trans-isomers, which could impart improved performancewhen the precursors are converted to downstream compositions (e.g., insurfactants). New C₁₈ difunctional quaternized fatty amines andderivatives are also potentially available from oil or C₁₀ unsaturatedacid or ester self-metathesis. In addition to an expanded variety ofprecursors, the unsaturation present in the precursors allows forfurther functionalization, e.g., by sulfonation or sulfitation.

SUMMARY OF THE INVENTION

In one aspect, the invention relates to a quaternary ammonium, betaine,or sulfobetaine composition derived from a fatty amine, wherein thefatty amine is made from a metathesis-derived C₁₀-C₁₇ monounsaturatedacid, octadecene-1,18-dioic acid, or their ester derivatives. In anotheraspect, the invention relates to a quaternary ammonium, betaine, orsulfobetaine composition derived from a fatty amidoamine, wherein theamidoamine is made by reacting a metathesis-derived C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives and an aminoalkyl-substituted tertiary amine such as DMAPA.The invention includes derivatives made by sulfonating or sulfitatingthe quaternized fatty amines or amidoamines. In one aspect, the esterderivative of the C₁₀-C₁₇ monounsaturated acid or octadecene-1,18-dioicacid is a lower alkyl ester. In other aspects, the ester derivative is amodified triglyceride made by self-metathesis of a natural oil or anunsaturated triglyceride made by cross-metathesis of a natural oil withan olefin. The quaternary ammonium, betaine, and sulfobetainecompositions and their sulfonated or sulfitated derivatives are valuablefor a wide variety of end uses, including cleaners, fabric treatment,hair conditioning, personal care (liquid cleansing products,conditioning bars, oral care products), antimicrobial compositions,agricultural uses, and oil field applications.

DETAILED DESCRIPTION OF THE INVENTION

In one aspect, the invention relates to a quaternary ammonium, betaine,or sulfobetaine composition derived from a fatty amine. The fatty amineis made from a metathesis-derived C₁₀-C₁₇ monounsaturated acid,octadecene-1,18-dioic acid, or their ester derivatives.

The C₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioic acid, or theirester derivatives used as a reactant is derived from metathesis of anatural oil. Traditionally, these materials, particularly theshort-chain acids and derivatives (e.g., 9-decylenic acid or9-dodecylenic acid) have been difficult to obtain except in lab-scalequantities at considerable expense. However, because of the recentimprovements in metathesis catalysts, these acids and their esterderivatives are now available in bulk at reasonable cost. Thus, theC₁₀-C₁₇ monounsaturated acids and esters are conveniently generated bycross-metathesis of natural oils with olefins, preferably α-olefins, andparticularly ethylene, propylene, 1-butene, 1-hexene, 1-octene, and thelike. Self-metathesis of the natural oil or a C₁₀ acid or esterprecursor (e.g., methyl 9-decenoate) provides the C₁₈ diacid or diesterin optimal yield when it is the desired product.

Preferably, at least a portion of the C₁₀-C₁₇ monounsaturated acid has“Δ⁹” unsaturation, i.e., the carbon-carbon double bond in the C₁₀-C₁₇acid is at the 9-position with respect to the acid carbonyl. In otherwords, there are preferably seven carbons between the acid carbonylgroup and the olefin group at C9 and C10. For the C₁₁ to C₁₇ acids, analkyl chain of 1 to 7 carbons, respectively is attached to C10.Preferably, the unsaturation is at least 1 mole % trans-Δ⁹, morepreferably at least 25 mole % trans-Δ⁹, more preferably at least 50 mole% trans-Δ⁹, and even more preferably at least 80% trans-Δ⁹. Theunsaturation may be greater than 90 mole %, greater than 95 mole %, oreven 100% trans-Δ⁹. In contrast, naturally sourced fatty acids that haveΔ⁹ unsaturation, e.g., oleic acid, usually have ˜100% cis-isomers.

Although a high proportion of trans-geometry (particularly trans-Δ⁹geometry) may be desirable in the metathesis-derived quaternizedcompositions of the invention, the skilled person will recognize thatthe configuration and the exact location of the carbon-carbon doublebond will depend on reaction conditions, catalyst selection, and otherfactors. Metathesis reactions are commonly accompanied by isomerization,which may or may not be desirable. See, for example, G. Djigoué and M.Meier, Appl. Catal. A: General 346 (2009) 158, especially FIG. 3. Thus,the skilled person might modify the reaction conditions to control thedegree of isomerization or alter the proportion of cis- andtrans-isomers generated. For instance, heating a metathesis product inthe presence of an inactivated metathesis catalyst might allow theskilled person to induce double bond migration to give a lowerproportion of product having trans-Δ⁹ geometry.

An elevated proportion of trans-isomer content (relative to the usualall-cis configuration of the natural monounsaturated acid or ester)imparts differential physical properties to quaternary ammonium,betaine, or sulfobetaine compositions made from them, including, forexample, modified physical form, melting range, compactability, andother important properties. These differences should allow formulatorsthat use the quaternary compositions greater latitude or expanded choiceas they use them in cleaners, fabric treatment, personal care,agricultural uses, and other end uses.

Suitable metathesis-derived C₁₀-C₁₇ monounsaturated acids include, forexample, 9-decylenic acid (9-decenoic acid), 9-undecenoic acid,9-dodecylenic acid (9-dodecenoic acid), 9-tridecenoic acid,9-tetradecenoic acid, 9-pentadecenoic acid, 9-hexadecenoic acid,9-heptadecenoic acid, and the like, and their ester derivatives.

Usually, cross-metathesis or self-metathesis of the natural oil isfollowed by separation of an olefin stream from a modified oil stream,usually by distilling out the more volatile olefins. The modified oilstream is then reacted with a lower alcohol, typically methanol, to giveglycerin and a mixture of alkyl esters. This mixture normally includessaturated C₆-C₂₂ alkyl esters, predominantly C₁₆-C₁₀ alkyl esters, whichare essentially spectators in the metathesis reaction. The rest of theproduct mixture depends on whether cross- or self-metathesis is used.When the natural oil is self-metathesized and then transesterified, thealkyl ester mixture will include a C₁₈ unsaturated diester. When thenatural oil is cross-metathesized with an α-olefin and the productmixture is transesterified, the resulting alkyl ester mixture includes aC₁₀ unsaturated alkyl ester and one or more C₁₁ to C₁₇ unsaturated alkylester coproducts in addition to the glycerin by-product. The terminallyunsaturated C₁₀ product is accompanied by different coproducts dependingupon which α-olefin(s) is used as the cross-metathesis reactant. Thus,1-butene gives a C₁₂ unsaturated alkyl ester, 1-hexene gives a C₁₄unsaturated alkyl ester, and so on. As is demonstrated in the examplesbelow, the C₁₀ unsaturated alkyl ester is readily separated from the C₁₁to C₁₇ unsaturated alkyl ester and each is easily purified by fractionaldistillation. These alkyl esters are excellent starting materials formaking the inventive quaternized fatty amine or amidoamine compositions.

Natural oils suitable for use as a feedstock to generate the C₁₀-C₁₇monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives from self-metathesis or cross-metathesis with olefins arewell known. Suitable natural oils include vegetable oils, algal oils,animal fats, tall oils, derivatives of the oils, and combinationsthereof. Thus, suitable natural oils include, for example, soybean oil,palm oil, rapeseed oil, coconut oil, palm kernel oil, sunflower oil,safflower oil, sesame oil, corn oil, olive oil, peanut oil, cottonseedoil, canola oil, castor oil, tallow, lard, poultry fat, fish oil, andthe like. Soybean oil, palm oil, rapeseed oil, and mixtures thereof arepreferred natural oils.

Genetically modified oils, e.g., high-oleate soybean oil or geneticallymodified algal oil, can also be used. Preferred natural oils havesubstantial unsaturation, as this provides a reaction site for themetathesis process for generating olefins. Particularly preferred arenatural oils that have a high content of unsaturated fatty groupsderived from oleic acid. Thus, particularly preferred natural oilsinclude soybean oil, palm oil, algal oil, and rapeseed oil.

A modified natural oil, such as a partially hydrogenated vegetable oil,can be used instead of or in combination with the natural oil. When anatural oil is partially hydrogenated, the site of unsaturation canmigrate to a variety of positions on the hydrocarbon backbone of thefatty ester moiety. Because of this tendency, when the modified naturaloil is self-metathesized or is cross-metathesized with the olefin, thereaction products will have a different and generally broaderdistribution compared with the product mixture generated from anunmodified natural oil. However, the products generated from themodified natural oil are similarly converted to inventive quaternizedfatty amine or amidoamine compositions.

An alternative to using a natural oil as a feedstock to generate theC₁₀-C₁₇ monounsaturated acid, octadecene-1,18-dioic acid, or their esterderivatives from self-metathesis or cross-metathesis with olefins is amonounsaturated fatty acid obtained by the hydrolysis of a vegetable oilor animal fat, or an ester or salt of such an acid obtained byesterification of a fatty acid or carboxylate salt, or bytransesterification of a natural oil with an alcohol. Also useful asstarting compositions are polyunsaturated fatty esters, acids, andcarboxylate salts. The salts can include an alkali metal (e.g., Li, Na,or K); an alkaline earth metal (e.g., Mg or Ca); a Group 13-15 metal(e.g., B, Al, Sn, Pb, or Sb), or a transition, lanthanide, or actinidemetal. Additional suitable starting compositions are described at pp.7-17 of PCT application WO 2008/048522, the contents of which areincorporated by reference herein.

The other reactant in the cross-metathesis reaction is an olefin.Suitable olefins are internal or α-olefins having one or morecarbon-carbon double bonds. Mixtures of olefins can be used. Preferably,the olefin is a monounsaturated C₂-C₁₀ α-olefin, more preferably amonounsaturated C₂-C₈ α-olefin. Preferred olefins also include C₄-C₉internal olefins. Thus, suitable olefins for use include, for example,ethylene, propylene, 1-butene, cis- and trans-2-butene, 1-pentene,isohexylene, 1-hexene, 3-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, and the like, and mixtures thereof.

Cross-metathesis is accomplished by reacting the natural oil and theolefin in the presence of a homogeneous or heterogeneous metathesiscatalyst. The olefin is omitted when the natural oil isself-metathesized, but the same catalyst types are generally used.Suitable homogeneous metathesis catalysts include combinations of atransition metal halide or oxo-halide (e.g., WOCl₄ or WCl₆) with analkylating cocatalyst (e.g., Me₄Sn). Preferred homogeneous catalysts arewell-defined alkylidene (or carbene) complexes of transition metals,particularly Ru, Mo, or W. These include first and second-generationGrubbs catalysts, Grubbs-Hoveyda catalysts, and the like. Suitablealkylidene catalysts have the general structure:M[X¹X²L¹L²(L³)_(n)]═C_(m)═C(R¹)R²where M is a Group 8 transition metal, L¹, L², and L³ are neutralelectron donor ligands, n is 0 (such that L³ may not be present) or 1, mis 0, 1, or 2, X¹ and X² are anionic ligands, and R¹ and R² areindependently selected from H, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, and functional groups. Any two or more of X¹, X², L¹, L²,L³, R¹ and R² can form a cyclic group and any one of those groups can beattached to a support.

First-generation Grubbs catalysts fall into this category where m=n=0and particular selections are made for n, X¹, X², L¹, L², L³, R¹ and R²as described in U.S. Pat. Appl. Publ. No. 2010/0145086 (“the '086publication”), the teachings of which related to all metathesiscatalysts are incorporated herein by reference.

Second-generation Grubbs catalysts also have the general formuladescribed above, but L¹ is a carbene ligand where the carbene carbon isflanked by N, O, S, or P atoms, preferably by two N atoms. Usually, thecarbene ligand is party of a cyclic group. Examples of suitablesecond-generation Grubbs catalysts also appear in the '086 publication.

In another class of suitable alkylidene catalysts, L¹ is a stronglycoordinating neutral electron donor as in first- and second-generationGrubbs catalysts, and L² and L³ are weakly coordinating neutral electrondonor ligands in the form of optionally substituted heterocyclic groups.Thus, L² and L³ are pyridine, pyrimidine, pyrrole, quinoline, thiophene,or the like.

In yet another class of suitable alkylidene catalysts, a pair ofsubstituents is used to form a bi- or tridentate ligand, such as abiphosphine, dialkoxide, or alkyldiketonate. Grubbs-Hoveyda catalystsare a subset of this type of catalyst in which L² and R² are linked.Typically, a neutral oxygen or nitrogen coordinates to the metal whilealso being bonded to a carbon that is α-, β-, or γ- with respect to thecarbene carbon to provide the bidentate ligand. Examples of suitableGrubbs-Hoveyda catalysts appear in the '086 publication.

The structures below provide just a few illustrations of suitablecatalysts that may be used:

Heterogeneous catalysts suitable for use in the self- orcross-metathesis reaction include certain rhenium and molybdenumcompounds as described, e.g., by J. C. Mol in Green Chem. 4 (2002) 5 atpp. 11-12. Particular examples are catalyst systems that include Re₂O₇on alumina promoted by an alkylating cocatalyst such as a tetraalkyl tinlead, germanium, or silicon compound. Others include MoCl₃ or MoCl₅ onsilica activated by tetraalkyltins.

For additional examples of suitable catalysts for self- orcross-metathesis, see U.S. Pat. No. 4,545,941, the teachings of whichare incorporated herein by reference, and references cited therein.

Fatty amines used to make the quaternized compositions of the inventioncan be made by reacting a metathesis-derived C₁₀-C₁₇ monounsaturatedacid, octadecene-1,18-dioic acid, or their ester derivatives with asecondary amine, followed by reduction of the resulting fatty amide.They can also be made reducing a metathesis-derived acid or esterderivative to a fatty alcohol, followed by amination of the fattyalcohol. Thus, intermediates to the fatty amines are metathesis-derivedfatty alcohols or fatty amides.

In one aspect, the ester derivative is a lower alkyl ester, especially amethyl ester. The lower alkyl esters are preferably generated bytransesterifying a metathesis-derived triglyceride. For example,cross-metathesis of a natural oil with an olefin, followed by removal ofunsaturated hydrocarbon metathesis products by stripping, and thentransesterification of the modified oil component with a lower alkanolunder basic conditions provides a mixture of unsaturated lower alkylesters. The unsaturated lower alkyl ester mixture can be used “as is” tomake fatty amide precursors for the fatty amines or it can be purifiedto isolate particular alkyl esters prior to making fatty amides.

In another aspect, the ester derivative is the metathesis-derivedtriglyceride discussed in the preceding paragraph. Instead oftransesterifying the metathesis-derived triglyceride with a loweralkanol to generate lower alkyl esters as described above, themetathesis-derived triglyceride, following olefin stripping, is reacteddirectly with a secondary amine to make a fatty amide mixture, which isthen reduced to give a fatty amine. Alternatively, themetathesis-derived triglyceride, following olefin stripping, is reducedto give a fatty alcohol mixture, which is then aminated to give thefatty amine mixture.

The skilled person will appreciate that “ester derivative” hereencompasses other acyl equivalents, such as acid chlorides, acidanhydrides, or the like, in addition to the lower alkyl esters andglyceryl esters discussed above.

In one synthetic approach, the metathesis-derived acid or esterderivative is reacted with a secondary amine to give a fatty amide,followed by reduction of the fatty amide to give the fatty amine.

Suitable secondary amines have a hydrogen and two hydrocarbyl groupsattached to nitrogen. The hydrocarbyl groups are preferably linear,branched, or cyclic C₁-C₂₀ alkyl, C₆-C₂₀ aryl, or C₇-C₂₀ arylalkyl. Morepreferably, both of the hydrocarbyl groups are C₁-C₆ alkyl groups.Suitable secondary amines include, for example, N,N-dimethylamine,N,N-diethylamine, N,N,-dipropylamine, diisopropylamine,N,N-dibutylamine, N-methyl-N-cyclohexylamine, N-methyl-N-phenylamine,N-methyl-N-benzylamine, or the like, and mixtures thereof.N,N-Dimethylamine is cost-effective and is particularly preferred.

Suitable secondary amines include etheramines. Thus, amines that arereaction products of ammonia or primary amines and an alkylene oxide,for example 0.1 to 20 molar equivalents of ethylene oxide, propyleneoxide, or the like, can be used. The amine can be, for instance, amonoalkylated derivative of a Jeffamine® M series polyether amine(product of Huntsman). In some instances of using an etheramine, it maybe necessary to mask any hydroxyl functionality as an appropriatederivative, either before or after formation of the amide, so as toenable the subsequent reduction of this amide.

Although the fatty amides are made using a well-known process, theproduct mixture is unique because of the unconventional starting mixtureof acid or ester derivatives. The reactants are typically reacted, withor without a catalyst under conditions effective to convert the startingacid, ester, or other derivative to an amide. The reaction temperatureis typically within the range of 40° C. to 300° C., preferably from 50°C. to 250° C., and more preferably from 50° C. to 200° C.

Reduction of the fatty amide to give a terminal amine is accomplishedusing well-known methods, including reactions with a hydride reducingagent (boranes, aluminum hydrides, borohydrides, or the like), orcatalytic hydrogenation. Suitable reducing reagents include, forexample, borane, borane dimethylsulfide, sodium borohydride/iodine,lithium cyanoborohydride, aluminum hydride, lithium aluminum hydride,diisobutylaluminum hydride, and the like. For additional examples, seeR. Larock, Comprehensive Organic Transformations: A Guide to FunctionalGroup Preparations (1989), pp. 432-434, and M. Smith and J. March,March's Advanced Organic Chemistry, 5^(th) ed. (2001), pp. 1549-1550.

In an alternative synthetic approach, the fatty amine is made by firstreducing the metathesis-derived acid or ester derivative to give a fattyalcohol, followed by amination of the fatty alcohol. Themetathesis-derived acid or ester derivative is reduced to a fattyalcohol using a metal hydride reagent (sodium borohydride, lithiumaluminum hydride, or the like), catalytic hydrogenation, or otherwell-known techniques for generating the fatty alcohol (see, e.g., U.S.Pat. Nos. 2,865,968; 3,193,586; 5,124,491; 6,683,224; and 7,208,643, theteachings of which are incorporated herein by reference). Amination isthen preferably performed in a single step by reacting the fatty alcoholwith ammonia or a primary or secondary amine in the presence of anamination catalyst. Suitable amination catalysts are well known.Catalysts comprising copper, nickel, and/or alkaline earth metalcompounds are common. For suitable catalysts and processes foramination, see U.S. Pat. Nos. 5,696,294; 4,994,622; 4,594,455;4,409,399; and 3,497,555, the teachings of which are incorporated hereinby reference.

In a preferred aspect of the invention, the fatty amine is a fattyamidoamine made by reacting a metathesis-derived C₁₀-C₁₇ monounsaturatedacid, octadecene-1,18-dioic acid, or their ester derivatives with anaminoalkyl-substituted tertiary amine. This provides a product havingtertiary amine functionality without the need to reduce a fatty amide toa fatty amine with a strong reducing agent. Suitableaminoalkyl-substituted tertiary amines have a primary amino group at oneterminus, an alkylene group, and a tertiary amine group at the other endof the molecule. The alkylene group is preferably a C₂-C₆ linear orbranched diradical such as ethylene, propylene, butylene, or the like.Thus, suitable aminoalkyl-substituted tertiary amines include, forexample, N,N-dimethyl-1,2-ethanediamine, N,N-dimethyl-1,3-propanediamine(DMAPA), N,N-diethyl-1,3-propanediamine, N,N-dimethyl-1,4-butanediamine,and the like. DMAPA is particularly preferred. The primary amine groupexhibits good reactivity with the acid or ester derivative, while theterminal tertiary amine is preserved in the product and provides a sitefor quaternization.

The relative amounts of secondary amine or aminoalkyl-substitutedtertiary amine reacted with the ester or acid reactants depends on thedesired stoichiometry and is left to the skilled person's discretion. Ingeneral, enough of the secondary amine (or aminoalkyl-substitutedtertiary amine) is used to react with most or all of the available acidor ester groups, i.e., preferably greater than 90%, and more preferablygreater than 95%, of the available acid or ester groups.

The tertiary amine group of the fatty amine or fatty amidoamine isquaternized to give a quaternary ammonium, betaine, or sulfobetainecomposition. Suitable quaternizing methods and reagents are well knownin the art. Common reagents include, for example, alkyl halides (methylchloride, methyl bromide), dialkyl sulfates, carbonates, or phosphates(dimethyl sulfate, diethyl sulfate, dimethyl carbonate), benzylchloride, acetyl chloride, ethylene oxide, and the like. Betaines aretypically made by reacting the fatty amine or amidoamine with anw-haloalkylcarboxylic acid or alkali metal salt thereof (e.g., sodiummonochloroacetate or potassium monochloropropionate) in the presence ofa strong base. Sulfobetaines can be made by combining the fatty amine oramidoamine with epichlorohydrin, followed by sulfation with sodiumbisulfite. An alternative procedure is outlined below in whichepichlorohydrin is first reacted with sodium bisulfite in the presenceof sodium hydroxide, and the fatty amine is added to that reactionmixture, followed by warming and neutralization, to give thesulfobetaine. In yet another approach, the sulfobetaine is made byreacting the fatty amine or amidoamine with an alkane sultone, as inU.S. Pat. No. 3,280,179. Detailed procedures are also provided below formaking the quats using dimethyl sulfate as the quaternizing agent, andfor making betaines using sodium monochloroacetate. Additionalquaternization details appear in U.S. Pat. Nos. 3,280,179, 3,354,213,4,743,660, 4,913,841, 5,679,150, 7,449,435, and 7,807,614, the teachingsof which are incorporated herein by reference.

Some quaternary ammonium compositions from the fatty amines have theformula:R²(R³)N⁺(R¹)R⁴X⁻

wherein:

R¹ is —C₁₀H₁₈—R⁵ or —C₁₈H₃₄—N⁺(R²)(R³)R⁴; each of R² and R³ isindependently substituted or unsubstituted alkyl, aryl, alkenyl,oxyalkylene, or polyoxyalkylene; R⁴ is C₁-C₆ alkyl; X⁻ is a halide,bicarbonate, bisulfate, or alkyl sulfate; and R⁵ is hydrogen or C₁-C₇alkyl. Preferably, R¹ is —(CH₂)₈—CH═CHR⁵ or—(CH₂)₈—CH═CH—(CH₂)₈—N⁺(R²)(R³)R⁴R⁴X⁻.

Some betaines or sulfobetaine compositions have the formula:R²(R³)N⁺(R¹)R⁴

wherein:

R¹ is —C₁₀H₁₈—R⁵ or —C₁₈H₃₄—N⁺(R²)(R³)R⁴; each of R² and R³ isindependently substituted or unsubstituted alkyl, aryl, alkenyl,oxyalkylene, or polyoxyalkylene; R⁴ is C₂-C₄ alkylene carboxylate, C₂-C₄alkylene sulfonate, or C₂-C₄ hydroxyalkylene sulfonate; and R⁵ ishydrogen or C₁-C₇ alkyl. Preferably, R¹ is —(CH₂)₈—CH═CHR⁵ or—(CH₂)₈—CH═CH—(CH₂)₈—N⁺(R²)(R³)R⁴.

Some quaternary ammonium compositions from the fatty amidoamines havethe formula:R⁴(R³)(R²)N⁺(CH₂)_(n)NH(CO)R¹X⁻

wherein: R¹ is —C₉H₁₆—R⁵ or —C₁₆H₃₀—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴X⁻; eachof R² and R³ is independently substituted or unsubstituted alkyl, aryl,alkenyl, oxyalkylene, or polyoxyalkylene; R⁴ is C₁-C₆ alkyl; X⁻ is ahalide, bicarbonate, bisulfate, or alkyl sulfate; R⁵ is hydrogen orC₁-C₇ alkyl; and n=2 to 8. Preferably, R¹ is —(CH₂)₇—CH═CH—R⁵ or—(CH₂)₇—CH═CH—(CH₂)₇—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴X⁻.

Some amidoamine betaine or sulfobetaine compositions have the formula:R⁴(R³)(R²)N⁺(CH₂)_(n)NH(CO)R¹

wherein:

R¹ is —C₉H₁₆—R⁵ or —C₁₆H₃₀—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴; each of R² andR³ is independently substituted or unsubstituted alkyl, aryl, alkenyl,oxyalkylene, or polyoxyalkylene; R⁴ is C₂-C₄ alkylene carboxylate, C₂-C₄alkylene sulfonate, or C₂-C₄ hydroxyalkylene sulfonate; R⁵ is hydrogenor C₁-C₇ alkyl; and n=2 to 8. Preferably, R¹ is —(CH₂)₇—CH═CH—R⁵ or—(CH₂)₇—CH═CH—(CH₂)₇—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴.General Note Regarding Chemical Structures:

As the skilled person will recognize, products made in accordance withthe invention are typically mixtures of cis- and trans-isomers. Exceptas otherwise indicated, all of the structural representations providedherein show only a trans-isomer. The skilled person will understand thatthis convention is used for convenience only, and that a mixture of cis-and trans-isomers is understood unless the context dictates otherwise.(The “C18-” series of products in the examples below, for instance, arenominally 100% trans-isomers whereas the “Mix-” series are nominally80:20 trans-/cis-isomer mixtures.) Structures shown often refer to aprincipal product that may be accompanied by a lesser proportion ofother components or positional isomers. For instance, reaction productsfrom modified triglycerides are complex mixtures. As another example,sulfonation or sulfitation processes often give mixtures of sultones,alkanesulfonates, and alkenesulfonates, in addition to isomerizedproducts. Thus, the structures provided represent likely or predominantproducts. Charges may or may not be shown but are understood, as in thecase of amine oxide structures. Counterions, as in quaternizedcompositions, are not usually included, but they are understood by theskilled person from the context.

Specific examples of C₁₀, C₁₂, C₁₄, and C₁₆-based quaternized fattyamines and fatty amidoamines appear below:

Some specific examples of C₁₈-based quaternized fatty amines and fattyamidoamines:

The quaternized fatty amine or fatty amidoamine product mixture can becomplex when the ester derivative reacted with the secondary amine oraminoalkyl-substituted tertiary amine is a modified triglyceride made byself-metathesis of a natural oil and separation to remove olefins (see,e.g., the MTG and PMTG products described below) or an unsaturatedtriglyceride made by cross-metathesis of a natural oil and an olefin andseparation to remove olefins (see, e.g., the UTG and PUTG productsdescribed below). As is evident from the reaction schemes, thequaternized MTG and PMTG products from DMAPA include an unsaturated C₁₈quaternized diamidoamine as a principal component, while the UTG andPUTG products include a C₁₀ unsaturated quaternized amidoamine and oneor more C₁₁ to C₁₇ unsaturated quaternized amidoamine components. (Forexample, with 1-butene as the cross-metathesis reactant, as illustrated,a C₁₂ unsaturated amidoamine component results.) Other components of theproduct mixtures are glycerin and saturated or unsaturated quaternizedDMAPA amides. Despite the complexity, purification to isolate aparticular species is often neither economical nor desirable for goodperformance.

Thus, in one aspect, a fatty amidoamine is quaternized. The fattyamidoamine is produced by reacting an aminoalkyl-substituted tertiaryamine with a modified triglyceride made by self-metathesis of a naturaloil. Self-metathesis of the natural oil provides a mixture of olefinsand a modified triglyceride that is enriched in a C₁₈ unsaturateddiester component along with C₁₈-C₁₈ saturated diesters. The olefins arestripped out, usually with heat and reduced pressure. When the modifiedtriglyceride is reacted directly with DMAPA, a complex mixture resultsin which primary amino groups of DMAPA completely or partially displaceglycerin from the glyceryl esters to form amidoamine functionalities.Representative amidoamine products below are made by reacting DMAPA withMTG-0 (modified triglyceride from soybean oil) or PMTG-0 (modifiedtriglyceride from palm oil) followed by quaternization. One example isthe MTG DMAPA sulfobetaine (“MTG-11”):

In another aspect, the fatty amidoamine is produced by reacting anaminoalkyl-substituted tertiary amine with an unsaturated triglyceridemade by cross-metathesis of a natural oil with an olefin.Cross-metathesis of the natural oil and olefin provides a mixture ofolefins and an unsaturated triglyceride that is rich in C₁₀ and C₁₂unsaturated esters as well as C₁₆-C₁₈ saturated esters. The olefins arestripped out, usually with heat and reduced pressure. When theunsaturated triglyceride is reacted directly with DMAPA, a complexmixture results in which primary amino groups of DMAPA completely orpartially displace glycerin from the glyceryl esters to form amidoaminefunctionalities. Representative amidoamine products below are made byreacting DMAPA with UTG-0 (unsaturated triglyceride fromcross-metathesis of soybean oil and 1-butene) or PUTG-0 (unsaturatedtriglyceride from cross-metathesis of palm oil with 1-butene), followedby quaternization. One example is the PUTG DMAPA dimethyl sulfate quatproduct (“PUTG-13”):

The reaction to form the amidoamines from lower alkyl esters can beperformed under a nitrogen sparge or under vacuum to remove liberatedalcohol. When glyceride esters are reactants, the liberated glycerinneed not be removed from the product. The reaction is consideredcomplete when the residual glyceride content of the product reaches thedesired level.

The quaternized fatty amines or amidoamines and their derivatives haveunsaturation that can be sulfonated or sulfitated if desired.Sulfonation is performed using well-known methods, including reactingthe olefin with sulfur trioxide. Sulfonation may optionally be conductedusing an inert solvent. Non-limiting examples of suitable solventsinclude liquid SO₂, hydrocarbons, and halogenated hydrocarbons. In onecommercial approach, a falling film reactor is used to continuouslysulfonate the olefin using sulfur trioxide. Other sulfonating agents canbe used with or without use of a solvent (e.g., chlorosulfonic acid,fuming sulfuric acid), but sulfur trioxide is generally the mosteconomical. The sultones that are the immediate products of reactingolefins with SO₃, chlorosulfonic acid, and the like may be subsequentlysubjected to a hydrolysis reaction with aqueous caustic to affordmixtures of alkene sulfonates and hydroxyalkane sulfonates. Suitablemethods for sulfonating olefins are described in U.S. Pat. Nos.3,169,142; 4,148,821; and U.S. Pat. Appl. Publ. No. 2010/0282467, theteachings of which are incorporated herein by reference.

Sulfitation is accomplished by combining an olefin in water (and usuallya cosolvent such as isopropanol) with at least a molar equivalent of asulfitating agent using well-known methods. Suitable sulfitating agentsinclude, for example, sodium sulfite, sodium bisulfite, sodiummetabisulfite, or the like. Optionally, a catalyst or initiator isincluded, such as peroxides, iron, or other free-radical initiators.Typically, the reaction mixture is conducted at 15-100° C. until thereaction is reasonably complete. Suitable methods for sulfitatingolefins appear in U.S. Pat. Nos. 2,653,970; 4,087,457; 4,275,013, theteachings of which are incorporated herein by reference.

The quaternized fatty amines, fatty amidoamines, and their sulfonated orsulfitated derivatives can be incorporated into many compositions foruse as, for example, surfactants, emulsifiers, skin-feel agents, filmformers, rheological modifiers, biocides, biocide potentiators,solvents, release agents, and conditioners. The compositions find valuein diverse end uses, such as personal care (liquid cleansing products,conditioning bars, oral care products), household products (liquid andpowdered laundry detergents, liquid and sheet fabric softeners, hard andsoft surface cleaners, sanitizers and disinfectants), and industrial orinstitutional cleaners.

The quaternized fatty amines or amidoamines and their derivatives can beused in emulsion polymerizations, including processes for themanufacture of latex. They can be used as surfactants, wetting agents,dispersants, or solvents in agricultural applications, as inertingredients in pesticides, or as adjuvants for delivery of pesticidesfor crop protection, home and garden, and professional applications. Thequaternized fatty amines or amidoamines and their derivatives can alsobe used in oil field applications, including oil and gas transport,production, stimulation and drilling chemicals, reservoir conformanceand enhancement uses, and specialty foamers. The compositions are alsovaluable as foam moderators or dispersants for the manufacture ofgypsum, cement wall board, concrete additives and firefighting foams.The compositions are used as coalescents for paints and coatings, and aspolyurethane-based adhesives.

In food and beverage processing, the quaternized fatty amines oramidoamines and their derivatives can be used to lubricate the conveyorsystems used to fill containers. When combined with hydrogen peroxide,the quaternized fatty amines or amidoamines and their derivatives canfunction as low foaming disinfectants and sanitization agents, odorreducers, and as antimicrobial agents for cleaning and protecting foodor beverage processing equipment. In industrial, institutional andlaundry applications, the quaternized fatty amines or amidoamines andtheir derivatives, or their combination with hydrogen peroxide, can beused to remove soil and sanitize and disinfect fabrics and asantimicrobial film-forming compositions on hard surfaces.

The following examples merely illustrate the invention. Those skilled inthe art will recognize many variations that are within the spirit of theinvention and scope of the claims.

Feedstock Syntheses Preparation of Methyl 9-Decenoate (“C10-0”) andMethyl 9-Dodecenoate (“C12-0”)

The procedures of U.S. Pat. Appl. Publ. No. 2011/0113679, the teachingsof which are incorporated herein by reference, are used to generatefeedstocks 010-0 and 012-0 as follows:

Example 1A Cross-Metathesis of Soybean Oil and 1-Butene

A clean, dry, stainless-steel jacketed 5-gallon Parr reactor equippedwith a dip tube, overhead stirrer, internal cooling/heating coils,temperature probe, sampling valve, and relief valve is purged with argonto 15 psig. Soybean oil (SBO, 2.5 kg, 2.9 mol, Costco, M_(n)=864.4g/mol, 85 weight % unsaturation, sparged with argon in a 5-gal containerfor 1 h) is added to the Parr reactor. The reactor is sealed, and theSBO is purged with argon for 2 h while cooling to 10° C. After 2 h, thereactor is vented to 10 psig. The dip tube valve is connected to a1-butene cylinder (Airgas, CP grade, 33 psig headspace pressure, >99 wt.%) and re-pressurized to 15 psig with 1-butene. The reactor is againvented to 10 psig to remove residual argon. The SBO is stirred at 350rpm and 9-15° C. under 18-28 psig 1-butene until 3 mol 1-butene per SBOolefin bond are transferred into the reactor (˜2.2 kg 1-butene over 4-5h).

A toluene solution of[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]-dichlororuthenium(3-methyl-2-butenylidene)(tricyclohexylphosphine)(0827, Materia) is prepared in a Fischer-Porter pressure vessel bydissolving 130 mg catalyst in 30 g of toluene (10 mol ppm per mol olefinbond of SBO). The catalyst mixture is added to the reactor via thereactor dip tube by pressurizing the headspace inside the Fischer-Portervessel with argon to 50-60 psig. The Fischer-Porter vessel and dip tubeare rinsed with additional toluene (30 g). The reaction mixture isstirred for 2.0 h at 60° C. and is then allowed to cool to ambienttemperature while the gases in the headspace are vented.

After the pressure is released, the reaction mixture is transferred to around-bottom flask containing bleaching clay (Pure-Flo® B80 CG clay,product of Oil-Dri Corporation of America, 2% w/w SBO, 58 g) and amagnetic stir bar. The reaction mixture is stirred at 85° C. underargon. After 2 h, during which time any remaining 1-butene is allowed tovent, the reaction mixture cools to 40° C. and is filtered through aglass frit. An aliquot of the product mixture is transesterified with 1%w/w NaOMe in methanol at 60° C. By gas chromatography (GC), it contains:methyl 9-decenoate (22 wt. %), methyl 9-dodecenoate (16 wt. %), dimethyl9-octadecenedioate (3 wt. %), and methyl 9-octadecenoate (3 wt. %).

The results compare favorably with calculated yields for a hypotheticalequilibrium mixture: methyl 9-decenoate (23.4 wt. %), methyl9-dodecenoate (17.9 wt/%), dimethyl 9-octadecenedioate (3.7 wt. %), andmethyl 9-octadecenoate (1.8 wt. %).

Example 1B

The procedure of Example 1A is generally followed with 1.73 kg SBO and 3mol 1-butene/SBO double bond. An aliquot of the product mixture istransesterified with sodium methoxide in methanol as described above.The products (by GC) are: methyl 9-decenoate (24 wt. %), methyl9-dodecenoate (18 wt. %), dimethyl 9-octadecenedioate (2 wt. %), andmethyl 9-octadecenoate (2 wt. %).

Example 1C

The procedure of Example 1A is generally followed with 1.75 kg SBO and 3mol 1-butene/SBO double bond. An aliquot of the product mixture istransesterified with sodium methoxide in methanol as described above.The products (by GC) are: methyl 9-decenoate (24 wt. %), methyl9-dodecenoate (17 wt. %), dimethyl 9-octadecenedioate (3 wt. %), andmethyl 9-octadecenoate (2 wt. %).

Example 1D

The procedure of Example 1A is generally followed with 2.2 kg SBO and 3mol 1-butene/SBO double bond. Additionally, the toluene used to transferthe catalyst (60 g) is replaced with SBO. An aliquot of the productmixture is transesterified with sodium methoxide in methanol asdescribed above. The products (by GC) are: methyl 9-decenoate (25 wt.%), methyl 9-dodecenoate (18 wt. %), dimethyl 9-octadecenedioate (3 wt.%), and methyl 9-octadecenoate (1 wt. %).

Example 1E

Separation of Olefins from Modified Triglyceride. A 12-L round-bottomflask equipped with a magnetic stir bar, heating mantle, and temperaturecontroller is charged with the combined reaction products from Examples1A-1D (8.42 kg). A cooling condenser with a vacuum inlet is attached tothe middle neck of the flask and a receiving flask is connected to thecondenser. Volatile hydrocarbons (olefins) are removed from the reactionproduct by vacuum distillation. Pot temperature: 22° C.-130° C.;distillation head temperature: 19° C.-70° C.; pressure: 2000-160 μtorr.After removing the volatile hydrocarbons, 5.34 kg of non-volatileresidue remains. An aliquot of the non-volatile product mixture istransesterified with sodium methoxide in methanol as described above.The products (by GC) are: methyl 9-decenoate (32 wt. %), methyl9-dodecenoate (23 wt. %), dimethyl 9-octadecenedioate (4 wt. %), andmethyl 9-octadecenoate (5 wt. %). This mixture is also called “UTG-0.”(An analogous product made from palm oil is called “PUTG-0.”)

Example 1F

Methanolysis of Modified Triglyceride. A 12-L round-bottom flask fittedwith a magnetic stir bar, condenser, heating mantle, temperature probe,and gas adapter is charged with sodium methoxide in methanol (1% w/w,4.0 L) and the non-volatile product mixture produced in Example 1E (5.34kg). The resulting light-yellow heterogeneous mixture is stirred at 60°C. After 1 h, the mixture turns homogeneous and has an orange color(pH=11). After 2 h of reaction, the mixture is cooled to ambienttemperature and two layers form. The organic phase is washed withaqueous methanol (50% v/v, 2×3 L), separated, and neutralized by washingwith glacial acetic acid in methanol (1 mol HOAc/mol NaOMe) to pH=6.5.Yield: 5.03 kg.

Example 1G

Isolation of Methyl Ester Feedstocks. A 12-L round-bottom flask fittedwith a magnetic stirrer, packed column, and temperature controller ischarged with the methyl ester mixture produced in example 1F (5.03 kg),and the flask is placed in a heating mantle. The glass column is 2″×36″and contains 0.16″ Pro-Pak™ stainless-steel saddles (Cannon InstrumentCo.). The column is attached to a fractional distillation head to whicha 1-L pre-weighed flask is fitted for collecting fractions. Distillationis performed under vacuum (100-120 μtorr). A reflux ratio of 1:3 is usedto isolate methyl 9-decenoate (“C10-0”) and methyl 9-dodecenoate(“C12-0”). Samples collected during the distillation, distillationconditions, and the composition of the fractions (by GC) are shown inTable 1. A reflux ratio of 1:3 refers to 1 drop collected for every 3drops sent back to the distillation column. Combining appropriatefractions yields methyl 9-decenoate (1.46 kg, 99.7% pure) and methyl9-dodecenoate (0.55 kg, >98% pure).

TABLE 1 Isolation of C10-0 and C12-0 by Distillation Head Distillationtemp. Pot temp. Vacuum Weight C10-0 C12-0 Fractions # (° C.) (° C.)(μtorr) (g) (wt %) (wt %) 1 40-47 104-106 110 6.8 80 0 2 45-46 106 11032.4 99 0 3 47-48 105-110 120 223.6 99 0 4 49-50 110-112 120 283 99 0 550 106 110 555 99 0 6 50 108 110 264 99 0 7 50 112 110 171 99 0 8 51 114110 76 97 1 9 65-70 126-128 110 87 47 23 10 74 130-131 110 64 0 75 11 75133 110 52.3 0 74 12 76 135-136 110 38 0 79 13 76 136-138 100 52.4 0 9014 76 138-139 100 25.5 0 85 15 76-77 140 110 123 0 98 16 78 140 100 4260 100

Precursor Syntheses C10-25: C10 DMA Amide

A round-bottom flask is charged with methyl ester feedstock C10-0 (235g) and the mixture is degassed with nitrogen. Sodium methoxide (5 g of30% solution in methanol) is added via syringe and the mixture isstirred for 5 min. Dimethylamine (67 g) is slowly added via sub-surfacedip tube. After the addition, the mixture is heated to 60° C. and heldovernight. The amide, C10-25, is recovered via vacuum distillation (120°C., 20 mm Hg). Yield: 241.2 g (96.3%). Iodine value=128.9 g I₂/100 gsample. ¹H NMR (CDCl₃), δ (ppm)=5.8 (CH₂═CH—); 4.9 (CH₂═CH—); 2.8-3.0(—C(O)—N(CH₃)₂); 2.25 (—CH₂—C(O)—). Ester content (by ¹H NMR): 0.54%.

C12-25: C12 DMA Amide

A round-bottom flask is charged with methyl ester C12-0 (900 g) and thefeedstock is degassed with nitrogen at 60° C. Sodium methoxide (30 g of30% solution in methanol) is added via syringe and the mixture isstirred for 5 min. Vacuum is then applied and the reaction vesselsealed. Dimethylamine (200 g) is slowly added via sub-surface dip tubeagainst the static vacuum. After the addition, the remaining vacuum isreleased with nitrogen, and the mixture is heated to 70° C. for 1 h. Themixture is heated to 80° C., DMA is sparged through the liquid for 2 h,and the mixture is then heated to 90° C. for 1 h. The sparge is stopped,and the reaction is cooled to 75° C. Full vacuum is applied and held for0.5 h. The vacuum is released, and 50% H₂SO₄ (16.3 g) and deionizedwater (200 mL) are added to quench the catalyst. The organic layer iswashed with deionized water (2×300 mL, then 1×150 mL) and then 20% brinesolution (50 mL). The organic layer is concentrated (full vacuum, 75°C.) and vacuum distilled (pot: 140-150° C.) to isolate amide C12-25.Iodine value: 112.8 g I₂/100 g sample; % moisture: 65 ppm. ¹H NMR(CDCl₃), δ (ppm): 5.35 (—CH═CH—); 2.8-3.0 (—C(O)—N(CH₃)₂; 2.25(—CH₂—C(O)—).

Amine Syntheses C10-38: C10 Amine

Amide C10-25 (475 g) is slowly added over 3 h to a stirring THF slurryof LiAlH₄ (59.4 g) under nitrogen while maintaining the temperature at11-15° C. The mixture warms to room temperature and stirs overnight. Themixture is chilled in an ice bath, and water (60 g) is added cautiously,followed by 15% aq. NaOH solution (60 g) and then additional water (180g) is added. The mixture warms to room temperature and is stirred for 1h. The mixture is filtered, and the filter cake is washed with THF. Thefiltrates are combined and concentrated. NMR analysis of the crudeproduct indicates that it contains approximately 16% 9-decen-1-ol, aside-product formed during the reduction of the amide. In order tosequester the alcohol, phthalic anhydride is to be added, thus formingthe half-ester/acid. The product mixture is heated to 60° C. andphthalic anhydride (57.5 g) is added in portions. NMR analysis of themixture shows complete consumption of the alcohol, and the mixture isvacuum distilled to isolate 010-38. Amine value: 298.0 mg KOH/g; iodinevalue: 143.15 g I₂/100 g sample; % moisture: 0.02%. ¹H NMR (CDCl₃), δ(ppm): 5.8 (CH₂═CH—); 4.9 (CH₂═CH—); 3.7 (—CH₂—N(CH₃)₂).

C12-26: C12 Amine

The procedure used to make C10-38 is generally followed with amideC12-25 (620 g) and LiAlH₄ (67.8 g). When the reaction is complete, water(68 g) and 15% aq. NaOH solution (68 g) and water (204 g) are used toquench the reaction. After the usual filtration and concentration steps,NMR analysis of the crude product shows approximately 16% 9-dodecen-1-olto be present. And phthalic anhydride (30 g) is added in order tosequester the alcohol. The mixture is then vacuum distilled to giveC12-26. Amine value: 258.1 mg KOH/g sample; iodine value: 120.0 g I₂/100g sample. ¹H NMR (CDCl₃), δ: 5.35 (—CH═CH—); 2.2 (—CH₂—N(CH₃)₂).

Amidoamine Syntheses C10-17: C10 DMAPA Amide

A round-bottom flask is charged with methyl ester C10-0 (500 g), DMAPA(331 g), and sodium methoxide/MeOH solution (0.5 wt. % sodium methoxidebased on the amount of methyl ester). The contents are heated slowly to140° C. and held for 6 h. The reaction mixture is vacuum stripped (110°C. to 150° C.). After cooling to room temperature, the product, C10-17,is analyzed. Amine value: 224.1 mg KOH/g; iodine value: 102.6 g I₂/100 gsample; titratable amines: 99.94%. ¹H NMR (CDCl₃), δ (ppm): 5.75(CH₂═CH—); 4.9 (CH₂═CH—); 3.3 (—C(O)—NH—CH₂—); 2.15 (—N(CH₃)₂).

C12-17: C12 DMAPA Amide

A round-bottom flask is charged with methyl 9-dodecenoate (“C12-0,” 670g). The mixture is stirred mechanically, and DMAPA (387 g) is added. ADean-Stark trap is fitted to the reactor, and sodium methoxide (30 wt. %solution, 11.2 g) is added. The temperature is raised to 130° C. over1.5 h, and methanol is collected. After 100 g of distillate isrecovered, the temperature is raised to 140° C. and held for 3 h. ¹H NMRshows complete reaction. The mixture is cooled to room temperatureovernight. The mixture is then heated to 110° C. and DMAPA is recoveredunder vacuum. The temperature is slowly raised to 150° C. over 1.5 h andheld at 150° C. for 1 h. The product, amidoamine C12-17, is cooled toroom temperature. Amine value: 202.1 mg KOH/g; iodine value: 89.5 gI₂/100 g sample; free DMAPA: 0.43%; titratable amines; 100.3%. ¹H NMR(CDCl₃), δ: 5.4 (—CH═CH—); 3.3 (—C(O)—NH—CH₂—); 2.2 (—N(CH₃)₂).

C10 Amine Derivatives C10-42: C10 Amine DMS Quat

Amine C10-38 (90.1 g) and isopropyl alcohol (50 g) are charged to aflask under nitrogen, and the stirred mixture is warmed to 60° C.Dimethyl sulfate (59.23 g) is added dropwise with air cooling tomaintain a reaction temperature of 60-70° C. Additional dimethyl sulfate(0.4 g) is added to ensure full conversion. The mixture is held at 70°C. for 3 h, then at 85° C. for 1 h. On cooling, C10-42 is analyzed: pH:9.15 (1% in 9:1 IPA/water); free amine: 0.057 meq/g; moisture: 0.05 wt.%; IPA: 24.4 wt. %.

C10-40: C10 Benzyl Quat

A flask equipped with a condenser and nitrogen inlet is charged withC10-17 (86.56 g) and methanol (30 g). The mixture is warmed to 80° C.and benzyl chloride (56.37 g) is added. The temperature is raised to 82°C. for 1 h. On cooling, C10-40 is analyzed: pH: 8.6 (1% in 9:1IPA/water); methanol: 17.5 wt. %; iodine value: 67.37; free amine: 0.065meq/g; tertiary amine: 0.0169 meq/g; active alkyl quat: 2.645 meq/g.

C10-41: C10 Betaine

A flask is charged with C10-38 (114 g), water (180 mL), and sodiummonochloroacetate (74.6 g). The mixture is heated to 100° C. and the pHis maintained at 7-9 by adding 50% NaOH. After 6 h, titration shows 9.7%chloride (theoretical: 10%). Upon cooling, C10-41 is analyzed: moisture:49.58%; NaCl=9.95%. ¹H NMR (D₂O), δ: 5.8 (CH₂═CH—); 4.9 (CH₂═CH—); 3.7(—CH₂—N⁺(CH₃)₂); 3.1 (—CH₂—N⁺(CH₃)₂).

C10-43: C10 Amine Sulfobetaine

A flask equipped with nitrogen inlet is charged with sodiummetabisulfite (50 g) and water (197 g), and the mixture is warmed to 40°C. Aqueous sodium hydroxide (0.6 g of 50% solution) is added. Afterstirring the mixture 5 min., epichlorohydrin (47.7 g) is added dropwiseover 1 h, and the reaction exotherms to 70° C. The mixture is stirred at70° C. for another 0.5 h. More aq. NaOH solution (0.6 g) is added andthe mixture stirs briefly. Amine C10-38 (90 g) is added, and thetemperature is increased to 90° C. After 1 h, the temperature isincreased to 95° C. and held at 90-95° C. for 11.5 h. The pH is keptbetween 8.3 and 8.7 with 50% NaOH (aq) charges (2×1 g and 1×0.75 g). Thereaction is judged complete when the NaCl level stabilizes at 7.60%. Themixture is cooled to give C10-43 as a clear solution (369.7 g). Analysisshows: pH: 7.53 (10% as is in DI water); NaCl: 7.82 wt. %; moisture:48.8 wt. %. ¹H NMR analysis supports the proposed structure (multipletat ˜4.7 for the methine proton, CH—OH).

C12 Amine Derivatives C12-45: C12 Amine DMS Quat

A flask equipped with nitrogen inlet is charged with amine C12-26 (95.5g), and the contents are warmed to 60° C. Dimethyl sulfate (54.28 g) isadded dropwise. The mixture is cooled to maintain a temperature from65-70° C. During the addition, a precipitate forms, and isopropylalcohol (26.4 g) is added. The mixture is stirred at 70° C. for 3 h.Additional dimethyl sulfate (0.55 g) is added to ensure a completeconversion, and the mixture is stirred at 70° C. for 3 h, then at 85° C.for 1 h. The product, C12-45, is analyzed: pH: 6.36 (1% in 9:1IPA/water); free amine: 0.040 meq/g; moisture: 0.4 wt. %; IPA: 11.6 wt.%.

C12-27: C12 Amine Benzyl Quat

A round-bottom flask equipped with a magnetic stir bar, nitrogen inlet,thermocouple, condenser, and addition funnel is charged with amineC12-26 (92.77 g, 0.439 mol) and methanol (30 g). The mixture is warmedto 67° C. and benzyl chloride (52.77 g, 0.417 mol) is slowly added. Moremethanol (6.5 g) is added during the benzyl chloride addition. Thereaction temperature is slowly raised to 82° C. After 2 h, free amineremains (by ¹H NMR), so more benzyl chloride (1.6 g, 0.0126 mol) isadded. The mixture stirs at 82° C. for 2 h. The product, C12-27, iscooled and analyzed: iodine value: 44.97; tertiary amine: 0.53%;methanol: 19.3 wt. %; free amine: 0.043 meq/g; moisture: 0.14 wt. %;active alkyl quat: 2.38 meq/g. ¹H NMR analysis supports the proposedstructure (singlet at ˜4.9 ppm for the benzyl methylene).

C12-40: C12 Betaine

Amine C12-26 (117.7 g), water (342.9 g), and sodium monochloroacetate(66 g) are combined and heated to 100° C. The pH is maintained from 7-9by adding 50% NaOH solution. After 7.5 h, titration shows 0.387% freeamine. The mixture is cooled and neutralized to pH ˜7 with 50% H₂SO₄.Analysis of the product, C12-40, shows: moisture: 63.8%; NaCl: 7.04%;free amine: 0.014 meq/g. ¹H NMR (d₄-MeOH), δ: 5.3 (—CH═CH—); 3.7(—C(O)—CH₂—N⁺(CH₃)₂—); 3.1 (—C(O)—CH₂—N⁺(CH₃)₂—).

C12-46: C12 Amine Sulfobetaine

The procedure used to make sulfobetaine C10-43 is generally followedwith amine C12-26 (100 g), sodium metabisulfite (48 g), water (203.5 g),50% aq. NaOH (two 0.6-g portions), and epichlorohydrin (45.9 g). Afteraddition of the tertiary amine, the reaction mixture is heated at 90-95°C. for a total of 10.5 hours while keeping the pH between 7.9 and 8.6with 50% NaOH (aq) charges (2.3 g, 1 g, and 1 g) and monitoring NaCllevel. After 8.5 h, the NaCl level stabilizes well below the expectedtheoretical value. 3-Chloro-2-hydroxypropanesulfonate, sodium salthydrate (2.7 g) is added, and the mixture is held at 95° C. for anadditional 2 h. The NaCl level stabilizes at 7.24% and the reaction isjudged complete and cooled to room temperature. The pH of the productsolution is adjusted to 8.1 with a small quantity of 50% H₂SO₄. Theproduct, C12-46, is analyzed: pH: 7.53 (10% as is in deionized water);NaCl: 7.82 wt. %; moisture: 48.8 wt. %. ¹H NMR analysis of a driedaliquot supports the proposed structure (multiplet at ˜4.7 for themethine proton, CH—OH).

C10 Amidoamine Derivatives C10-18: C10 DMAPA Quat

A flask equipped with condenser and nitrogen inlet is charged withamidoamine 010-17 (151.3 g). After warming to 80° C., dimethyl sulfate(68.38 g) is added dropwise. The temperature is raised to 85° C. and themixture is stirred for 2 h. Isopropyl alcohol (23.45 g) is added, andthe mixture stirs for 1 h. The product, 010-18, is analyzed: IPA: 7.72wt. %; pH: 8.41 (1% in 9:1 IPA/water); iodine value: 56.8; tertiaryamine: 0.020 meq/g; moisture: 1.7 wt. %; quaternary actives: 91.2 wt. %.

C10-19: C10 DMAPA Quat Sulfonate

Methyl quat C10-18 (98.30 g) and water (216.3 g) are charged to around-bottom flask equipped with stir bar, condenser, and thermocouple.The mixture is heated at 80° C. until homogeneous. Sodium metabisulfite(Na₂S₂O₅; 23.49 g, 1.03 eq. NaHSO₃) is added, and the mixture is held at80° C. overnight. ¹H NMR (D₂O) shows ˜50% conversion to the sulfitatedproduct. The mixture is held at 80° C. for 48 h and then reanalyzed;there are no significant changes. Sulfur dioxide is bubbled through themixture, which is then held at 80° C. overnight, but there are still nosignificant changes in the NMR spectrum. The reaction stirs at roomtemperature over the weekend. The pH is adjusted to 6.6 and the mixtureis heated at 80° C. overnight. NMR analysis shows that olefin peaks havediminished. The pH has dropped to 3 and is adjusted with caustic to 7.After heating for another 24 h, NMR analysis shows no more changes, with˜4-5% olefin remaining. Additional sodium metabisulfite (0.91 g, 0.04eq. NaHSO₃) is added, and the reaction mixture is heated overnight. The¹H NMR spectrum indicates complete conversion to the desired quatsulfonate, C10-19. Analysis shows: moisture: 60.1%; Na₂SO₄: 1.93%.

C10-31: C10 DMAPA Benzyl Quat

A round-bottom flask equipped with a stir bar, reflux condenser andthermocouple, is charged with amidoamine C10-17 (250.3 g) and methanoland heated to 67° C. Benzyl chloride (44 g) is added dropwise withheating removed at the start of the addition. The addition rate isadjusted to keep the temperature below 95° C. After benzyl chlorideaddition is complete, the temperature is adjusted to 82° C. and held for2 h. Aqueous sodium hydroxide (0.33 g of 50% solution) is added,followed by more benzyl chloride (7 g), and the mixture is held at 82°C. for 2 h. ¹H NMR shows the desired product benzyl quat. The mixture iscooled to room temperature and diluted with water (67 g). The resultingquat product, 010-31 (239 g), is analyzed: iodine value: 41.87; pH:10.96 (as is); moisture: 27.9 wt. %; actives: 65.1 wt. %; tertiaryamine: 0.0012 meq/g; methanol: 10.0 wt. %. ¹H NMR analysis supports theproposed structure (singlet at ˜4.3 ppm for the benzyl methylene).

C10-22: C10 DMAPA Betaine

Amidoamine C10-17 (120 g), water (222.4 g), and sodium monochloroacetate(57.5 g) are charged to a round-bottom flask, and the contents areheated to 80° C. for 1 h. The pH (10% reaction mixture in water orisopropyl alcohol) is controlled between 8.5 and 10 using 50% aq. NaOHsolution. The temperature is increased to 100° C. for 5 h with acondenser and nitrogen sparge included. Chloride titration is used toevaluate reaction completeness. After 5 h, hydrochloric acid is used toadjust pH to 7. The mixture is cooled and the product, C10-22, isanalyzed: NaCl: 7.39%; free amine: 0.5%.

C10-23: C10 DMAPA Betaine Sulfonate

A round-bottom flask is charged with water (54 g) and sodium sulfite(14.3 g), and the pH adjusted to 6.6 with aqueous NaOH solution. Themixture is heated to 75° C. and tert-butylperoxybenzoate (36 μL) isadded. After 30 min., betaine 010-22 (123 g) is added, followed bytert-butylperoxybenzoate (0.12 mL). The homogeneous mixture ismaintained at pH=7 with sulfur dioxide. After 16 h, ¹H NMR indicatescomplete consumption of starting material, and the betaine sulfonateproduct, C10-23, is cooled to room temperature. Analysis shows:moisture: 62.9%; Na₂SO₄: 1.96%; free NaCl: 4.54%; free sulfite: 0.65%.

C10-24: C10 DMAPA Sulfobetaine

The procedure used to make sulfobetaine C10-43 is generally followedwith amidoamine C10-17 (60 g), sodium metabisulfite (25.6 g), water (114g), 50% aq. NaOH (two 0.3-g portions), and epichlorohydrin (24.4 g).Reaction continues at 75° C. for 3 h, and the pH (10% aqueous dilution)is kept between 8.2 and 8.9. After 3 h, the mixture cools to roomtemperature overnight. The mixture is reheated to 75° C. After 1 h, thepH has fallen to 8.1 and is increased with 50% NaOH (0.3 g). Reactioncontinues for 1 h. The reaction is judged complete when the NaCl levelstabilizes at 6.55%. The mixture cools to room temperature, and the pHis adjusted to 6.95 with 50% H₂SO₄. The sulfobetaine product, C10-24, isanalyzed: NaCl: 6.55 wt. %; solids: 51.8%; sulfobetaine actives (bysolids-NaCl): 45.25%. ¹H NMR analysis of a dried aliquot of the productmixture supports the proposed structure.

C12 Amidoamine Derivatives C12-18: C12 DMAPA Quat

A flask equipped with condenser and nitrogen inlet is charged withamidoamine C12-17 (155.8 g), which is warmed to 80° C. Dimethyl sulfate(68.38 g) is added dropwise. The reaction temperature is raised to 85°C. and held for 1 h, then to 95° C. for 3 h. Isopropyl alcohol (24.9 g)is added, and the mixture stirs for 1 h. Analysis of the quat product,C12-18, shows: IPA: 8.9 wt. %; iodine value: 53.95; pH: 8.07 (1% in 9:1IPA/water); moisture: 0.6 wt. %.

C12-19: C12 DMAPA Quat Sulfonate

Methyl quat C12-18 (57.88 g) and water (115 g) are charged to around-bottom flask and gently heated until homogeneous. Hydrogenperoxide (35% aq. H₂O₂, 4 drops) is added. Oxygen is bubbled through thesolution, and Na₂S₂O₅ (12.62 g) is added in equal portions over 9 h. Themixture then stirs for 24 h. The pH is adjusted to 5 with dilute aq.NaOH. Analysis by ¹H NMR shows 70% sulfate and 30% unreacted startingmaterial. Analysis of the product shows: moisture: 60.1%; Na₂SO₄: 1.34%;free bisulfite: 10 mg/L.

C12-41: C12 DMAPA Benzyl Quat

Amidoamine C12-17 (104.2 g) is charged to a reaction flask equipped withthermocouple, reflux condenser, mechanical stirrer, addition funnel, andnitrogen inlet. Methanol (28.1 g) is added, and the stirred solution isheated to 65° C. The heating mantle is removed, and benzyl chloride(40.99 g) is added dropwise, allowing the reaction temperature toincrease on its own. After the benzyl chloride addition is complete,heating resumes, and the temperature is adjusted to 80° C. Reactioncontinues for 3.25 h. The mixture cools to room temperature overnight.The reaction mixture is rewarmed to 50° C. for 3 h. Additional benzylchloride (0.92 g) is added, and the mixture is heated to 80° C. for 2 h.Deionized water (99 g) is added with stirring at 50° C., and thesolution cools to room temperature. The benzyl quat, C12-41 (266.0 g) isanalyzed: pH: 9.2 (1% in 9:1 IPA/water); free tertiary amine HCl: 0.089wt. %; free amine: 0.47 wt. %; moisture: 35.9 wt. %; actives: 54.0 wt.%. ¹H NMR analysis supports the proposed structure (singlet at ˜4.5 ppmfor the benzyl methylene group).

C12-22: C12 DMAPA Betaine

A round-bottom flask is charged with amidoamine C12-17 (210 g) and water(400 g). Sodium monochloroacetate (89 g) is added, and the mixture isheated to 80° C. The pH is maintained between 8 and 10 with 50% aq. NaOH(measuring pH as a 10% solution in water using pH strips). Thetemperature is raised to 100° C. and held for 4 h. The mixture is cooledto room temperature overnight. Water (100 g) is added to dilute themixture, which is reheated to 100° C. for 4 h. Chloride titration shows5.55% NaCl (expected 5.62%). The product, betaine C12-22, is cooled andanalyzed: moisture: 62.13%; NaCl: 5.66%; free amine: 2.28%. ¹H NMR(d₄-MeOH), δ: 5.4 (—CH═CH—); 3.8 (—C(O)—CH₂—N⁺(CH₃)₂—); 3.2(—C(O)—CH₂—N⁺(CH₃)₂—).

C12-23: C12 DMAPA Betaine Sulfonate

Betaine C12-22 (284.6 g) is combined with water and sodium sulfite (33mg). Air is bubbled through the solution at 0.5 mL/min. With stirring atroom temperature, portions of sodium metabisulfite (5.99 g) are addedevery hour for 4 h, and the resulting solution stirs overnight. ¹H NMRindicates 74% conversion. Additional sodium metabisulfite (2.39 g) isadded, and the reaction is stirred overnight. 1H NMR shows 77%conversion. The product, sulfonate C12-23, is analyzed: moisture: 77.2%;Na₂SO₄: 1.6%; free bisulfite: 10 mg/L.

C12-24: C12 DMAPA Sulfobetaine

The procedure used to make sulfobetaine C10-24 is generally followedwith amidoamine C12-17 (105 g), sodium metabisulfite (39.6 g), water(190 g), 50% aq. NaOH (two 0.6-g portions), and epichlorohydrin (37.8g). Reaction continues at 80° C. for 3.5 h, and the pH (10% aqueousdilution) is kept between 8.2 and 8.6. After 3.5 h, the mixture cools toroom temperature overnight. The mixture is reheated to 80° C. After 2 h,the pH is 8.5 and the NaCl level is 6.36%. The reaction is judgedcomplete. The mixture cools to room temperature, and the pH is adjustedto 7.6 with 50% H₂SO₄. The sulfobetaine product, C12-24, is analyzed:NaCl: 6.34 wt. %; moisture: 49.7%; solids: 50.4%; sulfobetaine actives(by solids-NaCl): 44.0%. ¹H NMR analysis of a dried aliquot of theproduct mixture supports the proposed structure.

Preparation of Methyl 9-Hexadecenoate (“C16-0”) feedstock

The procedures of Example 1A is generally followed except that 1-octeneis cross-metathesized with soybean oil instead of 1-butene. Combinedreaction products are then stripped as described in Example 1E to removethe more volatile unsaturated hydrocarbon fraction from the modified oilfraction. The procedure of Example 1F is used to convert the modifiedoil fraction to a methyl ester mixture that includes methyl9-hexadecenoate. Fractional distillation at reduced pressure is used toisolate the desired product, methyl 9-hexadecenoate from other methylesters.

C16-10: C16 DMAPA Quat

A flask equipped with condenser and nitrogen inlet is charged with thecorresponding C16 amidoamine C16-9 (105.5 g, prepared generally as inC12-17). After warming to 80° C., dimethyl sulfate (39.4 g) is addeddropwise keeping the temperature <90° C. After the addition, IPA (20 g)is added to thin the product. The temperature is reduced to 70° C. andthe mixture is stirred for 2 h. Analysis by perchloric acid titration(PAT) gives a value of 0.069 meq/g KOH (target=0.065 meq/g KOH) and thetemperature is increased to 85° C. and held for 3 h. The product,C16-10, cools to room temperature, giving a waxy solid. Analysis shows:IPA: 10.6%; pH (90/10 IPA/H₂O): 6.7; moisture: 0.23%; free tertiaryamine: 0.065 meq/g KOH; quat actives: 1.66 meq/g KOH.

C16-13: C16 DMAPA Betaine

Amidoamine C16-9 (126.6 g, prepared generally as in C12-17), sodiummonochloroacetate (SMCA, 44.7 g), and water (237 g) are charged to around-bottom flask equipped with mechanical stirring, thermocouple,temperature controller, nitrogen inlet, and condenser. The mixture isheated to 80° C. with good agitation and becomes clear afterapproximately an hour. The pH (determined as 10% in water using teststrips) is maintained between 8 and 10 by adding portions of 50% aq.NaOH as needed. As the reaction progresses, the mixture gels and water(100 g) is added to thin the mixture. The temperature is raised to 95°C. and held for 4 h. Analysis by 1H NMR shows complete conversion toDMAPA betaine C16-13. NaCl: 4.44%; moisture: 55.5%; free tertiary amine:0.70%.

C16-14: C16 DMA Amide

Methyl ester C16-0 (502 g, 1.8 mol) is charged to a vessel equipped withmechanical stirring, thermocouple, vacuum gauge and distillationsidearm. The material is heated to 50° C. and full vacuum is applied for30 min. to dry and degas the system. The vessel is backfilled withnitrogen and sodium methoxide (30% solution in methanol, 20 g) ischarged via syringe. The mixture is stirred 5 min. and then the pressureis reduced to approximately −25″ Hg. The vessel is sealed under staticvacuum and addition of dimethylamine (DMA) via sub-surface dip-tube isinitiated. When the pressure in the vessel equalizes, the distillationsidearm is connected to a water trap/bubbler and charging continues atatmospheric pressure, adjusting the rate of addition to minimize blow-by(indicated by bubbling in scrubber). When a slight excess of DMA hasbeen charged, the vessel is stirred for 3 h at 60° C. under nitrogen. ¹HNMR analysis indicates complete consumption of the methyl ester, and themixture is cooled to room temperature overnight. The mixture is reheatedto 65° C. and vacuum-stripped to remove excess DMA and MeOH. Whenstripping is complete, the vessel is backfilled with nitrogen.Concentrated HCl is added in portions until a moistened pH test stripindicates a slightly acidic pH. After stirring 15 min., the neutralizedmixture is washed with water (3×200 mL), adding 20% NaCl as needed tofacilitate phase separation. The washed product is heated to 65° C. andvacuum is slowly applied to remove water. When stripping is complete,the vessel is backfilled with nitrogen and the stripped product isfiltered through a plug of silica gel on a glass frit to remove a fineprecipitate. The product remains hazy, and it is diluted with ethylacetate and filtered again through a pad of diatomaceous earth, giving aclear yellow liquid. Volatiles are removed via rotary evaporator, thenunder high vacuum, affording dimethylamide C16-14 as a light yellow oil(509.4 g; 96.8% yield). ¹H NMR analysis is consistent with the targetstructure and shows 0.8% methyl ester remaining. Further analysis shows:moisture: 0.04%; iodine value: 89.3 g I₂/100 g sample.

C16-15: C16 Amine

Amide C16-14 (358.8 g) is slowly added over 3 h to a stirring THF slurryof LiAlH₄ (37.5 g) under nitrogen while maintaining the temperature at11-15° C. The mixture warms to approximately 20° C. and stirs 2 h. Themixture is chilled in an ice bath, and water (37.5 g) is addedcautiously, followed by 15% aq. NaOH solution (37.5 g) and thenadditional water (112.5 g) is added. The mixture warms to roomtemperature and is stirred for 1 h. The mixture is filtered, and thefilter cake is washed with THF. The filtrates are combined andconcentrated. Phthalic anhydride (20 g) is added in portions, and themixture is vacuum distilled to isolate C16-15. ¹H NMR analysis of theproduct shows approximately 6.5% fatty alcohol by-product remaining, andthe product is subsequently treated with additional phthalic anhydride,and then redistilled as above. Amine value: 187.8 mg KOH/g; iodinevalue: 94.4 g l₂/100 g sample; % moisture: 0.02%. ¹H NMR (CDCl₃), δ(ppm): 5.8 (CH₂═CH—); 4.9 (CH₂═CH—); 3.7 (—CH₂—N(CH₃)₂).

C16-16: C16 Betaine

A round-bottom flask equipped with mechanical stirrer, thermocouple,temperature controller, heating mantle, and pH probe is charged withamine C16-15 (123.2 g), water (200 g), and sodium monochloroacetate(64.6 g). The milky reaction mixture is heated to 80° C. for 1 h,maintaining pH between 7 and 10 by addition of 50% aq. NaOH. Thereaction mass is then heated to 95° C.; after an additional 1 h, themixture becomes clear and begins to thicken. Additional water (50 g) isadded and NaOH is added to maintain pH between 7 and 8. After 4 h totaltime at 95° C., the reaction mixture is allowed to cool. ¹H NMR (sampledried, dissolved in MeOD) indicates complete consumption of sodiummonochloroacetate and 75% conversion of amine to quaternary ammonium.The reaction mixture is re-heated to 95° C. and more sodiummonochloroacetate (6 g) is added. Again, the pH is maintained between 7and 8 by adding 50% aq. NaOH. After 1.5 h, ¹H NMR indicates 85%conversion of amine and a trace of residual chloroacetate. Water (50 mL)and sodium monochloroacetate (7.2 g) are added to the thick mixture.After 1 h, NMR indicates 92% amine conversion. More sodiummonochloroacetate (1.9 g) is added. After 1 h, conversion is 95.6%. ThepH is adjusted to 7.6 with aq. NaOH, and the mixture is heated 4 h at95° C. At this point, ¹H NMR indicates 98.2% conversion of amine. Themixture is cooled to 60° C. and the light-colored, thick betaineproduct, C16-16, is analyzed: moisture: 60.0%; free tertiary amine:0.024 meq/g; NaCl: 7.19%.

C16-17: C16 Amine Benzyl Quat

Amine C16-15 (70.0 g) is charged to a flask equipped with athermocouple, reflux condenser, mechanical stirrer, addition funnel, andnitrogen inlet. Methanol (25.2 g) is added with stirring, and thesolution is heated to 65° C. Benzyl chloride (30.3 g) is added dropwiseover ˜45 min., allowing the internal temperature to increase to ˜72° C.The reaction temperature is adjusted to 80° C., held for 4 h, thencooled to room temperature and allowed to stand overnight undernitrogen. On cooling, the reaction mixture gels, and additional methanol(5 g) is added. The mixture is heated to 50° C. Analysis by NMR shows noresidual benzyl chloride, but indicates a small quantity of freetertiary amine. Additional benzyl chloride (0.94 g) is added and themixture is stirred at 80° C. for 4 h. Analysis by ¹H NMR confirms acomplete reaction. The mixture is cooled and the benzyl quat, C16-17, isanalyzed: moisture: 2.83%; free tertiary amine: 0.0015 meq/g; alkylquaternary actives=2.28 meq/g.

Feedstock Synthesis Preparation of Dimethyl 9-Octadecene-1,18-dioate(“Mix-0” or “C18-0”)

Eight samples of methyl 9-dodecenoate (10.6 g each, see Table 2) arewarmed to 50° C. and degassed with argon for 30 min. A metathesiscatalyst([1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichlororuthenium(3-methyl-2-butenylidene)-(tricyclohexylphosphine),product of Materia) is added to the methyl 9-dodecenoate (amountindicated in Table 2) and vacuum is applied to provide a pressure of <1mm Hg. The reaction mixture is allowed to self-metathesize for the timereported. Analysis by gas chromatography indicates that dimethyl9-octadecene-1,18-dioate is produced in the yields reported in Table 2.“Mix-0” is an 80:20 trans-/cis-isomer mixture obtained from the reactionmixture. Crystallization provides the all-trans-isomer feed, “C18-0.”

TABLE 2 Self-Metathesis of Methyl 9-Dodecanoate Catalyst LoadingReaction C18-0 Sample (ppm mol/mol)* Time (h) (GC Area %) A 100 3 83.5 B50 3 82.5 C 25 3 83.0 D 10 3 66.2 E 15 4 90.0 F 13 4 89.9 G 10 4 81.1 H5 4 50.9 *ppm mol catalyst/mol methyl 9-dodecenoate

C18-26: C18 DiDMAPA Amide (100% trans-)

Dimethyl ester C18-0 (545.6 g), DMAPA (343.3), and sodium methoxidesolution (1.1 wt. % NaOMe based on methyl ester) are combined, heatedslowly to 150° C., and held 10.5 h. Additional DMAPA (100 mL) is added,and the mixture is heated to 150-160° C. for 4 h, then stirred overnightat 125° C. Additional 30% sodium methoxide in MeOH (10 g) is added, andthe mixture is heated at 155-160° C. for 4 h. More DMAPA (50 mL) isadded, and the mixture is heated at 180° C. for 2 h. The mixture iscooled to 110-120° C., concentrated HCl was added, and the contents arestirred vigorously for 15 min. The heating mantle is removed, and whenthe temperature reaches 90° C., deionized water is added to trituratethe product. The slurry cools to room temperature and is filtered. Thesolids are washed several times with water. The diamide product, C18-26,is analyzed: melting point: 97-101° C.; amine value: 230.4 mg KOH/g;free DMAPA: 0.08%; moisture: 0.08%; titratable amines: 98.95%. ¹H NMR(CDCl₃), δ (ppm): 5.35 (—CH═CH—); 3.3 (—C(O)—NH—CH₂—); 2.2 (—N(CH₃)₂).

Mix-26: C18 DiDMAPA Amide (80% trans, 20% cis)

Dimethyl ester C18-0 (824.3 g), DMAPA (519.5 g), and sodium methoxidesolution (2.4 wt. % NaOMe based on methyl ester) are heated slowly to140° C. and held for several hours. A subsurface nitrogen sparge isutilized at the end to facilitate the removal of methanol. Thetemperature is reduced to 100° C., and the contents are vacuum stripped.A solution made from deionized water (1.0 L) and 50% H₂SO₄ (11 g) isadded slowly to the molten reaction product. The mixture cools, and thepasty solids are isolated by filtration. The solids are washed withdeionized water, and the filtrate is extracted with chloroform (2×250mL). The chloroform extracts are concentrated, and the resulting yellowoil is identified as the cis-enriched product by ¹H NMR. The yellow oilis redissolved in CHCl₃, filtered through silica, and combined with thepasty solids. Additional CHCl₃ (100 mL) is added to the contents, andthe mixture is swirled on a rotary evaporator at 70° C. untilhomogeneous. Vacuum is applied, and the CHCl₃ is removed, followed bywater. Evaporation is discontinued when the product remains a solid at98° C. The cooled product, Mix-26, is analyzed: amine value: 229.1 mgKOH/g sample; free DMAPA: 0.08%; moisture: 0.09%; total alkalinity: 4.08meq/g. ¹H NMR (CDCl₃), δ (ppm)=5.3 (—CH═CH—); 3.25 (—C(O)—NH—CH₂—); 2.2(—N(CH₃)₂). ¹³C NMR (CDCl₃), δ (ppm)=130 (trans —CH═CH—); 129.5 (cis,—CH═CH—). Product ratio: 79.3% trans, 20.7% cis.

C18-27: C18 DiDMAPA DiQuat (100% trans-)

A flask equipped with nitrogen inlet is charged with diamide C18-26(83.0 g) and isopropyl alcohol (68.8 g), and the mixture is warmed to70° C. Additional IPA (49.11 g) is added to give a homogeneous solution.Dimethyl sulfate (92.0 g) is added. The outer flask is air cooled andthe addition rate is adjusted to keep the reaction temperature ˜70° C.The mixture stirs at 70° C. for 3 h, then at 85° C. for 3 h. Theresulting diquat product, C18-27, is analyzed: iodine value: 14.52; pH:7.72 (1% in 9:1 IPA/water); IPA: 28.1 wt. %; free amine: 0.055 wt. %;moisture: 0.48 wt. %; actives (alkyl quat): 73.0 wt. %.

Mix-27: C18 DiDMAPA DiQuat (80:20 trans-/cis-)

A flask equipped with condenser and nitrogen inlet is charged withdiamide Mix-26 (157.3 g), which is warmed to 80° C. Dimethyl sulfate(68.38 g) is added dropwise. The reaction temperature is raised to 85°C. and the mixture is stirred for 2 h. Isopropyl alcohol (23.45 g) isadded, and the mixture stirs for 1 h. The diquat product, Mix-27, isanalyzed: IPA: 7.72 wt. %; pH: 8.41 (1% in 9:1 IPA/water); iodine value:56.76; tertiary amine: 0.020 meq/g; moisture: 1.7 wt. %; quaternaryactives: 91.2 wt. %.

C18-28: C18 DiDMAPA DiQuat Sulfonate (100% trans-)

Diquat C18-27 (216.5 g), Na₂S₂O₅ (42.75 g), water (400.5 g), andt-butylperoxybenzoate (0.44 g) are combined and heated with stirring at75° C. for 18 h. ¹H NMR indicates 96% conversion. Isopropyl alcohol(from the C18-27 starting material) is stripped. The quat sulfonate,C18-28, is analyzed: moisture: 60.7%; Na₂SO₄: 2.85%; free sulfite:1.48%.

C18-31: C18 DiSulfobetaine (100% trans-)

A nitrogen-purged flask is charged with sodium metabisulfite (42.3 g)and water (190 g), and the mixture is warmed to 40° C. Aqueous sodiumhydroxide (0.6 g of 50% solution) is added. The mixture stirs briefly,and epichlorohydrin (40.4 g) is added dropwise over 1 h. The mixture isallowed to exotherm to 60° C. The mixture stirs at 70° C. for 0.5 h, andmore 50% NaOH (0.6 g) is added. After brief stirring, diamide C18-26(100 g) is added in one portion. The ensuing exotherm warms the mixtureto 80° C. The temperature is held at 80° C. and the mixture stirs for3.5 h. The pH is kept between 8.2 and 8.6 with 50% NaOH. After 3.5 h,the NaCl content of the mixture is 6.75%. The mixture cools to roomtemperature overnight. The mixture is reheated to 80° C. After 0.5 h,the pH is 8.1, and 50% NaOH (aq.) is used to raise the pH to 9.1. After1 h, the NaCl level remains at 6.75% and the reaction is judgedcomplete. The mixture cools to room temperature and the pH is adjustedto 7.94 with 50% aq. H₂SO₄. Analysis of the sulfobetaine, C18-31, shows:NaCl: 6.83 wt. %; moisture: 51.0%; solids: 49.0%; sulfobetaine actives(by solids-NaCl): 42.2%. ¹H NMR analysis of a dried aliquot of theproduct mixture supports the proposed structure.

Mix-31: C18 DiSulfobetaine (80:20 trans-/cis-)

The procedure used to make C18-31 is generally followed with diamideMix-26 (96 g), sodium metabisulfite (40.7 g), water (175 g), 50% aq.NaOH (two 0.5-g portions), and epichlorohydrin (38.8 g). The temperatureis held at 75° C. and the mixture stirs for 3 h. The pH is kept between8.3 and 8.7 with 50% NaOH. The mixture cools to room temperatureovernight. The mixture is reheated to 75° C. After 0.5 h, the pH is 8.2,and 50% NaOH (aq.) is used to raise the pH to 8.8. The mixture stirs anadditional 4.5 h at 75° C. The NaCl level is 6.81% and the reaction isjudged complete. The mixture cools to room temperature and the pH isadjusted to 8.0 with 50% aq. H₂SO₄. Analysis of the sulfobetaine,Mix-31, shows: NaCl: 6.94 wt. %; moisture: 48.9%; solids: 51.1%;sulfobetaine actives (by solids-NaCl): 44.1%. ¹H NMR analysis of a driedaliquot of the product mixture supports the proposed structure.

C18-32: C18 DiBetaine (100% trans-)

Diamide C18-26 (224.0 g) is charged to a flask, followed by water (614.3g) and sodium monochloroacetate (106 g). The mixture is heated to 100°C. and the pH is kept from 7-9 by adding 50% NaOH. After 3 h, titrationshows 0.038% free amine and 5.68% NaCl. The mixture is cooled,neutralized to pH ˜8 with 50% H₂SO₄, and analyzed: moisture: 65.4%;NaCl: 5.68%; free amine: 1.4 meq/g. ¹H NMR (d₄-MeOH), δ: 5.25 (—CH═CH—);3.7 (—C(O)—CH₂—N⁺(CH₃)₂—); 3.05 (—C(O)—CH₂—N⁺(CH₃)₂—).

Mix-32: C18 DiBetaine (80:20 trans-/cis-)

Diamide Mix-26 (128.17 g) is charged to a flask, followed by water(282.0 g) and sodium monochloroacetate (62.8 g). The mixture is heatedto 100° C. and the pH is kept from 7-9 by adding 50% NaOH. After severalhours, titration shows 6.53% free NaCl. The mixture is cooled,neutralized to pH ˜8 with 50% H₂SO₄, and analyzed: moisture: 59.7%;NaCl: 6.68%; free amine: 0.031 meq/g.

C18-33: C18 DiBetaine Sulfonate (100% trans-)

Dibetaine C18-32 (447.7 g of 32% active), Na₂S₂O₅ (23.45 g), water (197g), Na₂SO₃ (0.78 g), and t-butylperoxybenzoate (0.24 g) are combined andstirred at 80° C. for 17.5 h while adjusting the pH to ˜6 with periodicadditions of NaOH. ¹H NMR indicates 70% conversion. Water (100 mL) andadditional catalyst are added and heating continues for 5.5 h, thenovernight. ¹H NMR indicates that conversion to the sulfonate is 82%complete. The sulfonate, C18-33, is analyzed: moisture: 68.8%; Na₂SO₄:1.70%; NaCl: 4.18%; sulfites (by test strip): 200-400 mg sulfite/L.

C18-34: C18 DiDMAPA MonoQuat (100% trans-)

A round-bottom flask is charged with diamine C18-26 (225.8 g), which ispurged with nitrogen and heated to 70° C. Isopropyl alcohol (105.26 g)is added. Dimethyl sulfate (DMS) (58.8 g) is then added slowly viaaddition funnel so that the temperature is maintained around 70° C.After the DMS addition is complete, the mixture is held at 70° C. for 3h and then at 85° C. for 1 h. Free amine (by PAT): 1.199 meq/g.Theoretical expected PAT value for 50% quaternization of availabletertiary amine is 1.196 meq/g.

Mix-34: C18 DiDMAPA MonoQuat (80:20 trans-/cis-)

The procedure used to make C18-34 is generally followed with diamineMix-26 (241.6 g), isopropyl alcohol (98.4 g), and dimethyl sulfate (60g). After the DMS addition is complete, the reaction was held at 70° C.for 3 h and then at 85° C. for 3 h. Perchloric acid titration shows1.317 meq/g of free amine. ¹H NMR analysis (CD₃OD) shows 49% free amineand 51% quaternized amine, based on the integration of the methyl groupsignals at 2.25 and 3.11 ppm, respectively.

C18-35: C18 DiDMAPA Quat AO (100% trans-)

Amine monoquat C18-34 (75% solids, 192.3 g), deionized water (205.0 g),and Hamp-Ex 80 (0.5 g) are charged to a round-bottom flask. The mixtureis heated to 70° C., adjusting pH to >8 with citric acid. Aqueous H₂O₂(35%, 22.86 g) is added dropwise, maintaining temperature below 70° C.After peroxide addition is complete, the mixture is maintained at 70° C.for 20 h. ¹H NMR indicates complete conversion of tertiary amine toamine oxide. The mixture is cooled to room temperature. Titration shows:amine oxide: 0.50 meq/g; free amine: 0.042 meq/g; cationic actives: 0.62meq/g; free peroxide: 0.08%; and water: 55.8%.

Mix-35: C18 DiDMAPA Quat AO (80:20 trans-/cis-)

Mix-34 (186.9 g) is dissolved in deionized water (200 g) and stripped ofisopropyl alcohol at 75° C. The concentrate (321.6 g) is transferred toa round-bottom flask and Hamp-Ex 80 (0.53 g) is added. The mixture isheated to 50° C. and a few pieces of dry ice are added until the mixturepH is 8-9. Aqueous H₂O₂ (35%, 18.23 g) is then added dropwise,maintaining temperature below 70° C. After peroxide addition iscomplete, the mixture is maintained at 85° C. for 16 h. Deionized water(75 g) is added. The mixture cools to room temperature. ¹H NMR analysisis consistent with the proposed structure for quat amine oxide Mix-35and shows no detectable free amine. Other analyses show: free peroxide:0.002%; water: 59.2%.

C18-36: C18 DiDMAPA MonoBetaine (100% trans-)

Amidoamine C18-26 (348 g) and deionized water (500 g) are charged to around-bottom flask. The mixture is heated to 80° C. and citric acid (2.5g) is added. A solution made from sodium monochloroacetate (SMCA, 88.5g) and deionized water (300 g) is added dropwise to the amidoaminesolution over 1 h. After the addition is complete, the mixture is heatedto 85° C. for 3 h and then 95° C. for 0.5 h. The mixture is then cooledto room temperature. Analysis by silver nitrate titration indicates3.49% NaCl. Additional SMCA (1.5 g) is added and the mixture is reheatedto 95° C. for 6 h. After 6 h, the NaCl content is 3.53%. ¹H NMR analysisof a dried aliquot of product shows 45.7% free amine and 54.3%quaternized amine, based on the integration of the methyl group signalsat 2.28 and 3.22 ppm, respectively.

Mix-36: C18 DiDMAPA MonoBetaine (80:20 trans-/cis-)

The procedure used to make C18-36 is generally followed with amidoamineMix-26 (224.5 g), deionized water (322 g), citric acid (1.5 g), andaqueous sodium monochloroacetate (57 g of SMCA in 200 g of DI water).After the SMCA addition is complete, the mixture is heated to 90° C. for2 h. Additional SMCA (3.5 g) is added and the mixture is maintained at90° C. for 2 h. NaCl content: 3.82%. ¹H NMR analysis of a dried aliquotshows 44% free amine and 56% quaternized amine.

C18-37: C18 DiDMAPA Betaine AO (100% trans-)

Molten monobetaine C18-36 (35% solids, 415.2 g) is charged to a flaskand heated to 70° C. Aqueous H₂O₂ (35%, 23.6 g) is added dropwise over0.5 h, maintaining reaction temperature below 78° C. After the peroxideaddition is complete, the mixture is stirred at 70° C. for 9 h. ¹H NMR(CD₃OD) of a dried aliquot indicates complete conversion of themonobetaine to the expected amine oxide. Evidence is the disappearanceof the N(CH₃)₂ peak at 2.28 ppm for the amine and appearance of a peakat 3.15 ppm for the amine oxide N(CH₃)₂.

Mix-37: C18 DiDMAPA Betaine AO (80:20 trans-/cis-)

Monobetaine Mix-36 (35% solids, 470 g) is charged to a flask and heatedto 60° C. Aqueous H₂O₂ (35%, 27.6 g) is added dropwise over 0.5 h,maintaining the temperature at 70° C. After the addition is complete,the mixture is stirred at 70° C. for 3 h. A small quantity of partiallydried monobetaine (Mix-36) is added to react with excess peroxide. Themixture is maintained at 70° C. for 5 h. Free peroxide by titration:0.18%. ¹H NMR (CD₃OD) of a dried aliquot indicates complete conversionof the monobetaine to the expected amine oxide product. Integration ofthe amine oxide and betaine N(CH₃)₂ peaks indicates shows: betaine: 53.4mol %; amine oxide: 46.6 mol %.

C18-38: C18 DiDMAPA Betaine Quat (100% trans-)

A nitrogen-purged flask is charged with monobetaine C18-36 (138.9 g),isopropyl alcohol (40 g), and ethanol (42.5 g). The mixture is warmed to70° C. and dimethyl sulfate (21.77 g) is added dropwise. The mixture iscooled to maintain the temperature ˜70° C. The mixture is held at 70° C.for 6 h, then at 85° C. for 2 h. The mixture is allowed to cool and isconcentrated. Water is added to adjust the solids content to ˜50 wt. %.Analysis of the product, C18-38, shows: pH: 7.59; NaCl: 1.09 wt. %; IPA:0.49 wt. %; EtOH: 0.78 wt. %; moisture: 48.9 wt. %.

Mix-38: C18 DiDMAPA Betaine Quat (80:20 trans-/cis-)

A nitrogen-purged flask is charged with monobetaine Mix-36 (113.9 g),isopropyl alcohol (66 g), and ethanol (30 g). The mixture is warmed to70° C. and dimethyl sulfate (15.65 g) is added dropwise. The mixture iscooled to maintain the temperature ˜70° C. The mixture is held at 70° C.for 3 h. Additional dimethyl sulfate (0.96 g) is added, and heatingcontinues at 70° C. for 3 h, then at 85° C. for 2 h. The mixture isallowed to cool and is concentrated. Water (195 g) is added to ˜40 wt. %solids. Analysis of the betaine quat product, Mix-38, shows: pH: 8.35(1% in water); moisture: 47.7 wt. %; NaCl: 4.74 wt. %; sodium sulfate:0.3 wt. %. ¹H NMR data support the proposed structure.

Mix-69: C18 Ester/Acid (80:20 trans-/cis-)

The half-acid/ester Mix-69 is prepared from the dibasic ester Mix-0(used as received) as described in Organic Syntheses: Col. Vol. IV(1963) 635. Thus, Mix-0 (1 kg) is added to methanol (˜9 L) and themixture is stirred mechanically. In a separate vessel, Ba(OH)₂ (274.4 g)is dissolved in methanol (˜4 L), and the solution is added in portionsover 2 h to the stirred diester solution, resulting in the formation ofa white precipitate. The solid is isolated by filtration, washed severaltimes with methanol, and dried in air. The solid is then transferred toa 12-L reaction vessel and slurried in ethyl acetate (˜3.5 L). AqueousHCl (32%, Aldrich, 1248.6 g), is added in portions to the stirredslurry, resulting in dissolution of the solid and formation of a clearsolution. The solution is washed three times with water, and the aqueouslayers are removed and collected in a separate vessel. The combinedaqueous layers are extracted once with ethyl acetate, and the organicphase is combined with the washed product solution. The mixture is dried(Na₂SO₄), filtered, and concentrated via rotary evaporator. Thoroughdrying under high vacuum gives a waxy, crystalline solid upon cooling(655 g, ˜70% yield). Analysis of the product (following derivatization)by gas chromatography shows that it contains 94% acid/ester and 6%diacid. Quantitative ¹³C NMR shows an 86:14 trans:cis isomer ratio.

Mix-43: C18 Ester/DMAPA Amide (80:20 trans-/cis-)

The mixed acid/ester Mix-69 is converted to the acid chloride/ester byreaction with a slight excess of thionyl chloride (SOCl₂) in methylenechloride solution and the product is isolated by removal of the solventand excess SOCl₂ under reduced pressure. ¹H NMR analysis of the isolatedproduct shows essentially quantitative conversion to the acidchloride/ester, and the material is used without further purification.

A 3-L reaction vessel equipped with mechanical stirrer, nitrogen inlet,and thermocouple is charged with methylene chloride (200 mL), DMAPA(172.1 g), and pyridine (133.3 g). The previously prepared acidchloride/ester is added dropwise to the stirred DMAPA-pyridine solution.During the addition, the temperature is maintained at 25-40° C. bycooling with an ice bath as required, and the addition is completed in1.5 h. A precipitate forms, and after stirring overnight at roomtemperature, the mixture has become a thick slurry. The mixture isdiluted with methylene chloride (500 mL), and water (500 mL) is added,giving a clear homogeneous solution. Addition of ethyl acetate fails toinduce phase separation. However, addition of saturated NaCl solutioncauses slow separation of a lower aqueous phase, which is drained anddiscarded. Concentration of the organic phase via rotary evaporationgives a viscous brown oil. ¹H NMR analysis shows free pyridine andindicates that the terminal tertiary amine of the DMAPA moiety isprotonated. The material is taken up in acetone and the mixture isfiltered to remove a small quantity of precipitated solid. The pH of thesolution is adjusted to ˜8.5 (measured on as-is material) with 50% aq.NaOH, resulting in the formation of a solid precipitate. The mixture isfiltered again and the clear filtrate is concentrated and then driedunder high vacuum. On cooling, the material solidifies. ¹H NMR analysisis consistent with the target structure and shows the presence of freepyridine. The product is heated to 60° C., stirred, and sparged withsub-surface nitrogen under reduced pressure for 5 h, then at 105° C. for30 min. After stripping, ¹H NMR analysis of the product showed noresidual pyridine.

Mix-44: C18 Ester DMAPA Quat (80:20 trans-/cis-)

Ester-amidoamine Mix-43 (162.7 g) is charged to a flask equipped withmechanical stirring, thermocouple, and nitrogen inlet. Isopropanol (IPA;47.8 g) is added, and the mixture is heated to 70° C. Perchloric acidtitration of the ester/amide starting material is used to calculate therequired amount of dimethylsulfate (DMS). The DMS (28.6 g) is addeddropwise while maintaining the reaction temperature at 70° C. withexternal cooling. After the DMS addition is complete, the mixture isstirred at 70° C. for 3 h, then for 1 h at 85° C. Perchloric acidtitration shows nearly complete consumption of the tertiary amine. Thequat product, Mix-44, cools to give a waxy solid. Analysis for residualDMS via Drager apparatus is negative.

Mix-48: C18 Ester DMAPA Betaine (80:20 trans-/cis-)

A round-bottom flask fitted with a thermocouple, nitrogen inlet, andmechanical stirring is charged with ester-amidoamine Mix-43 (134.2 g,0.327 mol). Water (250 mL) and sodium monochloroacetate (38.9 g, 0.334mol) are added. The mixture is warmed to 70° C. and after approximately1 h, it becomes clear. During the reaction, the pH of the mixture ismaintained at ˜8 with 50% aq. NaOH. Heating continues for 5 h at 70° C.The ¹H NMR spectrum is consistent with the proposed structure and showsno residual tertiary amine. The product, ester-betaine Mix-48, is cooledand analyzed: water: 59.9%; NaCl: 4.29%.

C18-65: C18 DiDMAPA Benzyl Quat (100% trans-)

Bis(amidoamine) C18-26 (100 g) and methanol (67 g) are charged to aflask equipped with thermocouple, mechanical stirring, reflux condenser,and nitrogen inlet. The mixture is heated to 67° C. and benzyl chloride(44 gl is added dropwise while the temperature is allowed to rise to 82°C. During heat-up, the reflux condenser is replaced with a distillationside-arm and refluxing methanol distills from the mixture until thetemperature reaches 82° C. The side-arm is replaced with a refluxcondenser and the mixture stirs for 2 h at 82° C. Sodium hydroxide (50%aq., 0.33 g) is added, followed by more benzyl chloride (9 g), and themixture is held at 82° C. for 2 h. The mixture is cooled to 50° C. andpoured into water (67 g). After stirring for 5 min., the bis(benzylquat) solution is analyzed: methanol: 16.4%; free tertiary amine: nonedetected; water: 26.8%; quat actives: 58.7%. ¹H NMR spectrum isconsistent with the target structure.

Mix-65: C18 DiDMAPA Benzyl Quat (80:20 trans-/cis-)

A round-bottom flask equipped with a stir bar, reflux condenser, andthermocouple is charged with bis(amidoamine) C18-26 (118.4 g) andmethanol (44 g). The mixture is heated to 67° C. and benzyl chloride (50g) is added dropwise. The addition rate is adjusted to maintaintemperature below 95° C. After the benzyl chloride is added, thetemperature was adjusted to 82° C. and held for 2 h. More methanol (21g) is added to reduce viscosity. Sodium hydroxide (50% aq.; 0.33 g) isadded, followed by more benzyl chloride (11.2 g), and the mixture isheld at 82° C. for 2 h. 1H NMR analysis is consistent with the targetstructure and shows no residual tertiary amine. The hot benzyl quat isadded to deionized water (140 g) with good agitation, and the mixture isallowed to cool. Analysis of the bis(benzyl quat), Mix-65, shows: MeOH:10.8%; water: 39.7%; free tertiary amine: 0.027 meq/g; quat actives:49.1%.

Modified Triglyceride Based on Soybean Oil (“MTG-0”)

The procedures of Examples 1A and 1E are generally followed except that1-butene is omitted.

Mod. Triglyceride From Cross-Metathesis of Soybean Oil and 1-Butene(“UTG-0”)

The procedures of Examples 1A and 1E are generally followed to produceUTG-0 from soybean oil and 1-butene.

Modified Triglyceride Based on Palm Oil (“PMTG-0”)

The procedure used to make MTG-0 is followed, except that palm oil isused instead of soybean oil.

Mod. Triglyceride From Cross-Metathesis of Palm Oil and 1-Butene(“PUTG-0”)

The procedure used to make UTG-0 is followed, except that palm oil isused instead of soybean oil.

MTG-0 Feedstock Derivatives

TABLE 3 Summary of Modified Triglyceride Products Soybean Oil Palm OilSelf-met. X-met. Self-met. X-met. MTG-0 UTG-0 PMTG-0 PUTG-0 DMAPABetaine MTG-6 UTG-6 PMTG-6 PUTG-6 DMAPA Sulfobetaine MTG-11 UTG-11PMTG-11 PUTG-11 DMAPA DMS Quat MTG-13 UTG-13 PMTG-13 PUTG-13 DMAPABenzyl Quat MTG-14 UTG-14 PMTG-14 PUTG-14 DMAPA =N,N-dimethyl-1,3-propanediamine.

Detailed procedures appear below for preparation of the MTG and PUTGproducts starting from MTG-0 or PUTG-0. The PMTG products have analogousstructures to the MTG products. The UTG products have structuresanalogous to the PUTG products.

MTG-5: MTG DMAPA Amide Mix

A round-bottom flask is charged with MTG-0 (180 g, saponificationvalue=226.5 mg KOH/g, 0.73 mol), and the contents are heated to 50° C.The mixture is purged with nitrogen for 1 h and dimethylaminopropylamine(DMAPA, 78 g, 0.76 mol) and NaBH₄ (0.1 g) are added. The mixture isheated to 160° C. for 18 h. Excess amine is removed by short-pathdistillation (135° C., 30 mm Hg), and the product is cooled to roomtemperature to afford amidoamine mixture MTG-5. Amine value: 172.9 mgKOH/g (eq. wt.: 324.45 g/mol). Free DMAPA: 1.80%; iodine value: 71.9 gI₂/100 g sample.

MTG-6: MTG DMAPA Betaine Mix

A round-bottom flask is charged with MTG-5 (107.8 g, 0.32 mol), sodiummonochloroacetate (SMCA, 38.4 g, 0.33 mol), and water (237 g). Themixture is heated to 80° C. for 1 h, and the mixture becomeshomogeneous. The pH is maintained between 8.5-10 (measured as 10%dilution in IPA and/or water) using 50% aq. NaOH. After the pHstabilizes, the mixture is heated to 100° C. for 14 h. When the NaCllevel stabilizes, the reaction is judged complete. The product is cooledto room temperature, and the pH is adjusted to 8.5. The betaine product,MTG-6, is a clear, homogeneous solution. NaCl content: 5.22%; solids:39.4%; betaine actives: 34.2%.

MTG-11: MTG DMAPA Sulfobetaine

A nitrogen-purged flask is charged with sodium metabisulfite (46.4 g)and water (250 g), and the mixture is warmed to 40° C. Aqueous NaOH(0.75 g of 50% solution) is added and stirred briefly. Epichlorohydrin(44.3 g) is added dropwise over 1 h allowing the mixture to warm to 70°C. The mixture stirs at 70° C. for 0.5 h and more 50% NaOH (0.75 g) isadded. After briefly mixing, MTG-5 (150 g) is added in one portion. Themixture is held at 80° C. and stirred for 3 h. The pH is adjusted in theusual way from 8.2 to 10.3. After 3 h, the mixture cools to roomtemperature. The mixture is reheated to 80° C. and stirred for 1 h. WithpH=10.35 and NaCl content=6.81%, the reaction is judged complete. Theproduct cools to room temperature and the pH is adjusted to 8.60 with50% aq. H₂SO₄. Analysis of the sulfobetaine, MTG-11, shows: NaCl: 5.65wt. %; moisture: 49.7%; solids: 50.3%; sulfobetaine actives (bysolids-NaCl): 44.7%. ¹H NMR analysis of a dried aliquot supports theproposed structure.

MTG-13: MTG DMAPA DMS Quat

A nitrogen-purged flask is charged with MTG-5 (159.9 g) and the contentsare warmed to 80° C. Dimethyl sulfate (56.86 g) is added. The mixture iswarmed to 95° C., but viscosity remains high, so temperature is reducedto 70° C. and isopropyl alcohol (25.5 g) is added. The reaction stirsfor 3 h at 70° C. and is allowed to cool. Analysis of the quat product,MTG-13, shows: free amine: 0.055 meq/g; moisture: 0.13 wt. %; activequat: 1.80 meq/g.

MTG-14: MTG DMAPA Benzyl Quat

A round-bottom flask equipped with stir bar, reflux condenser, andthermocouple, is charged with MTG-5 (118.4 g) and methanol (23 g). Themixture is heated to 67° C. and benzyl chloride (39.3 g) is addeddropwise. The addition rate is adjusted to keep the temperature below95° C. After the addition, the temperature is adjusted to 82° C. andheld for 2 h. Aqueous sodium hydroxide (0.33 g of 50% solution) is addedfollowed by more benzyl chloride (6.9 g), and the mixture is held at 82°C. for 2 h. ¹H NMR shows the desired product. The hot benzyl quat isadded to water (140 g) and the mixture cools to room temperature whilestirring. The benzyl quat product, MTG-14 (300 g), is analyzed: pH: 6.7(1% in 9:1 in IPA/water); free amine: 0.011 meq/g; moisture: 42.9 wt. %;active quat: 1.06 meq/g; tertiary amine: 0.023 meq/g.

PUTG-5: PUTG DMAPA Amide Mix

Molten PUTG-0 (750 g, saponification value: 227.6 mg KOH/g, 3.04 mol) ischarged to a reaction vessel equipped with a reflux condenser,thermocouple, nitrogen/vacuum take-off, and mechanical agitator. Themixture is stirred at 60° C. under nitrogen. Sodium borohydride (0.4 g)is added, and the mixture is stirred for 0.5 h. The mixture is degassedunder full vacuum (0.5 h). The vacuum is released with nitrogen anddimethylaminopropylamine (DMAPA, 325 g, 3.18 mol) is then added. Thetemperature is increased until a gentle reflux of DMAPA occurs (˜150°C.). The mixture is held at 150° C. until reflux slows. The temperatureis then increased to 160° C. Stirring continues for 4 h at 160° C., andthen the mixture is stirred overnight at 150° C. The mixture is cooledto 100° C. and excess DMAPA is removed using a gentle vacuum and dry-icetrap. Vacuum is slowly improved until full vacuum is reached. Strippingcontinues for 1 h. The waxy product, PUTG-5, is titrated with HCl. Acidvalue: 160.6 meq/g; eq. wt.: 349.4 g/mol. Amine value: 160.56 mg KOH/g;% free DMAPA: 0.08%. ¹H NMR (CDCl₃), δ: 5.8 (CH₂═CH—); 5.4 (—CH═CH—);4.9 (CH₂═CH—); 3.2 (—C(O)—NH—CH₂—); 2.15 (—N(CH₃)₂).

PUTG-6: PUTG DMAPA Betaine Mix

Molten PUTG-5 (200 g, 0.57 mol) is charged to a reaction vessel, warmedto 50° C., and stirred mechanically while flushing the vessel withnitrogen for 0.5 h. A solution prepared from sodium monochloroacetate(SMCA, 0.58 mol, 68 g) and water (498 g) is added to the molten amine,and the temperature is increased to 70° C. The initially hazy mixturebecomes clear and homogeneous. The pH is maintained at 8.5-10 (measuredas 10% aqueous dilution) by adding 50% aqueous NaOH as requiredthroughout the reaction. The mixture is also analyzed for NaClperiodically to judge reaction completion. After 4 h, the temperature isincreased to 80° C. and held for 2 h before cooling to room temperatureovernight. NaCl content: 4.21% (theoretical NaCl based on 100%conversion: 4.45%). The mixture is reheated to 80° C. Free amine (bytitration): 0.43%. An additional charge of SMCA (1.10 g) is added, andstirring continues for 2 h at 80° C. Measured pH: 8.78; NaCl content:4.35%. The reaction is judged complete and the product, PUTG-6, iscooled to room temperature. ¹H NMR analysis of isolated solids isconsistent with the target structure. The final pH is adjusted to 7.5 byadding 50% H₂SO₄ (1 g), giving the product as a clear aqueous solution.Solids content: 35.8%; free amine: 0.85%; NaCl: 4.39%.

PUTG-11: PUTG DMAPA Sulfobetaine

The procedure used to make MTG-11 is generally followed with PUTG-5 (200g), sodium metabisulfite (61.1 g), water (330.8 g), 50% aqueous NaOH(two 1.0-g portions), and epichlorohydrin (58.3 g). After the mixturecools to room temperature, additional water (10 g) is added to the waxygel, and the mixture is reheated to 80° C. for 2.5 h. Again, the pH iskept between 8.4 and 9.2 with aqueous NaOH as required. When the NaCllevel stabilizes at 5.49%, the reaction is judged complete. Aftercooling to room temperature, the thick product is warmed to 40° C. andwater (15 g) is added. The pH is adjusted to 6.52 by adding 50% H₂SO₄(aq.). On cooling the product again becomes a thick gel, requiringfurther dilution. Additional water was added to give an approximately50% solids solution. The product, PUTG-11, is analyzed: NaCl: 5.29 wt.%; moisture: 51.2%; solids: 48.8%; sulfobetaine actives (bysolids-NaCl): 43.5%. ¹H NMR analysis of a dried aliquot supports theproposed structure.

PUTG-13: PUTG DMAPA DMS Quat

A nitrogen-purged flask is charged with PUTG-5 (113.3 g) and thecontents are warmed to 80° C. Dimethyl sulfate (40.23 g) is added. Themixture is warmed to 95° C. for 1 h. Viscosity remains high, andisopropyl alcohol (˜20 g) is added. The mixture stirs for 1 h and thencools to room temperature. Analysis of the quat product, PUTG-13, shows:pH: 7.47 (1% in 9:12-propanol/water); iodine value: 21.55, free amine:0.053 meq/g: moisture: 0.29 wt. %.

PUTG-14: PUTG DMAPA Benzyl Quat

A round-bottom flask equipped with stir bar, reflux condenser, andthermocouple, is charged with PUTG-5 (110 g) and methanol (21 g). Themixture is heated to 67° C. and benzyl chloride (34.4 g) is addeddropwise. The addition rate is adjusted to keep the temperature below95° C. After the addition, the temperature is adjusted to 82° C. andheld for 2 h. Aqueous sodium hydroxide (0.30 g of 50% solution) is addedfollowed by more benzyl chloride (5.5 g), and the mixture is held at 82°C. for 2 h. ¹H NMR shows the desired product. A gel forms, and themixture is rewarmed to 80° C. Water is added to give a clear solution,which is analyzed. The benzyl quat product, PUTG-14 (248 g), isanalyzed: iodine value: 10.22; pH: 9.15 (1% in 9:12-propanol/water);NaCl: 7.12 wt. %; moisture: 32.1 wt. %; tertiary amine: 0.22 wt. %;actives (alkyl quats): 1.23 meq/g.

Agricultural Glyphosate Formulations: Formulation Stability

Sample Preparation:

A 44.0% acid equivalent (a.e.) formulation is prepared by first chargingglyphosate acid (486.19 g, 90.5% a.e., product of Monsanto) to anice-cooled 1-L reaction vessel equipped with a mixer and temperatureprobe. Deionized water (337.23 g) is added with mixing to generate aglyphosate acid slurry. Potassium hydroxide pellets (176.58 g, 86.6%KOH, Fisher) are slowly added such that the temperature of the solutiondoes not exceed 50° C. The mixture is then allowed to cool to roomtemperature and is mixed until a clear glyphosate concentrate of 44%a.e. results. The pH of the concentrate is measured by preparing a 10%solution of the concentrate in deionized water and measuring it with apH electrode. If the pH of the concentrate is between 4.2 and 4.4 theconcentrate is used as is. If the pH needs to be adjusted, thenglyphosate acid, KOH, and water are added in appropriate quantities toyield the correct pH while maintaining the 44% a.e. level of theconcentrate required.

Stability Testing:

A test surfactant (5.0 g) is added to 45.0 g of the glyphosateconcentrate above (44% a.e.) to yield a glyphosate formulationconcentrate, ˜39.6% a.e. (˜540 g/L a.e. K salt). This concentrate ismixed until a clear solution results. If no clear solution results, analiquot of lauryl dimethyl amine oxide (LDMAO, ˜55-60% actives) is addedto the surfactant to make a 90:10 surfactant:LDMAO blend. This is thentested for stability as above. If that does not pass, the procedure ofadding LDMAO to the surfactant continues until a ratio is found thatgives a stable glyphosate formulation. If no stable formulation can bemade, the surfactant is deemed incompatible with glyphosate. If a clearhomogeneous solution results, the sample is split in two and placed bothin a 54° C. oven and a −10° C. freezer for two weeks. If there is nohaziness or separation, the formulation is considered stable at thattemperature.

The control surfactant is a C₁₂-C₁₄ DMEA esterquat. This is prepared byreacting a mixture of lauric (C₁₂) and myristic (C₁₄) acids with N,N-dimethylethanolamine (DMEA) at 140° C. for 5 h, then heating to 175°C. to complete the reaction. Quaternization with methyl chloride inpropylene glycol at 80° C. at 40 psig in the usual way provides thedesired esterquat. The control surfactant gives a clear formulation atroom temperature but the formulation separates at −10 C. Addition ofamine oxide in a 9:1 to 1:1 ratio (control surfactant to amine oxide) isneeded to give a desirable stability with the control.

As shown in Table 4, twenty-two samples performed as well as or betterthan similar compounds in the stability testing.

TABLE 4 Glyphosate Formulation Stability: 540 g.a.e./L K salts AO Stableat: Sample added RT −10° C. 54° C. Comment Rating C18-35 N Y Y Ysuperior Mix-35 N Y Y Y superior C18-36 N Y Y Y superior Mix-36 N Y Y Ysuperior C18-37 N Y Y Y superior Mix-44 N Y Y Y 5% sample superiorC10-41 Y Y Y Y 5% sample good C10-42 Y Y Y Y 5% sample good C12-18 Y Y YY 6% sample good C12-40 Y Y Y Y 5% sample good C12-45 Y Y Y Y 5% samplegood C16-13 Y Y Y Y 5% sample + good propylene glycol C16-16 Y Y Y Y 5%sample + good propylene glycol C18-27 Y Y Y Y 5% sample good Mix-27 Y YY Y 5% sample good C18-34 N Y Y Y 6% sample good Mix-37 N Y Y Y 5%sample good Mix-38 Y Y Y Y 5% sample good PMTG-13 N Y Y Y 60% sol. ingood propylene glycol passes PUTG-13 Y Y Y Y 5% sample good MTG-13 Y Y YY 6% sample, good 2.5% PG, 1.5% AO UTG-6 Y Y Y Y 5% sample goodWater-Soluble Herbicide Formulation Testing

Surfactant candidates for water soluble herbicide applications areexamined as a replacement for the anionic, nonionic, or anionic/nonionicblend portion and compared to a known industry standard for use inparaquat, a water soluble herbicide concentrate formulation. A standarddilution test is conducted whereby the concentrates are diluted in waterto determine if solubility is complete.

Control:

Paraquat (9.13 g of 43.8% active material) is added to a 20-mL glassvial. A known industry paraquat adjuvant (2.8 g) is added and vigorouslymixed for 30 s. Deionized water (8.07 g) is added, and mixing resumesfor 30 s. Standard 342 ppm water (47.5 mL) is added to a 50-mL Nesslercylinder, which is stoppered and equilibrated in a 30° C. water bath.Once the test water equilibrates, the formulated paraquat (2.5 mL) isadded by pipette into the cylinder. The cylinder is stoppered andinverted ten times. Solubility is recorded as complete or incomplete.Cylinders are allowed to stand and the amount (in mL) and type ofseparation are recorded after 30 min., 1 h, 2 h, and 24 h. Results ofthe solubility testing appear in Table 5 below.

Anionic Test Sample:

Paraquat (4.57 g of 43.8% active material) is added to a 20-mL glassvial. An eight to ten mole alkyl phenol alkoxylate surfactant (0.7 g) isadded and vigorously mixed for 30 s. Test sample (0.7 g) is added andmixing resumes for 30 s. Deionized water (4.03 g) is added, and mixingresumes for 30 s. A 2.5-mL sample of the formulated paraquat is added to47.5 mL of 342 ppm hardness water, and testing continues as describedabove for the control sample.

Nonionic Test Sample:

Paraquat (4.57 g of 43.8% active material) is added to a 20-mL glassvial. Test sample (0.7 g) is added and vigorously mixed for 30 s. Sodiumlinear alkylbenzene sulfonate (“NaLAS,” 0.7 g) is added and mixingresumes for 30 s. Deionized water (4.03 g) is added, and mixing resumesfor 30 s. A 2.5-mL sample of the formulated paraquat is added to 47.5 mLof 342 ppm hardness water, and testing continues as described above forthe control sample. See Table 5 for solubility results.

Adjuvant (Anionic/Nonionic) Test Sample:

Paraquat (4.57 g of 43.8% active material) is added to a 20-mL glassvial. Test sample (1.4 g) is added and vigorously mixed for 30 s.Deionized water (4.03 g) is added, and mixing resumes for 30 s. A 2.5-mLsample of the formulated paraquat is added to 47.5 mL of 342 ppmhardness water, and testing continues as described above for the controlsample. Criteria for emulsion solubility: Test samples should be as goodor better than the control with no separation after one hour.Thirty-three test samples perform as well as or better than the controlin the emulsion stability test. Results appear in Table 5.

TABLE 5 Water-Soluble Herbicide Formulation: Emulsion stability, mLseparation test Anionic Nonionic Adjuvant sample sol 1 h 24 h sol 1 h 24h sol 1 h 24 h Rating C10-19 S 0 0 D Tr 0.5 S 0 0 good C10-22 S 0 0 D Tr0.5 S 0 0 good C10-24 S 0 0 D 0.5 0.5 S 0 0 good C10-40 S 0 0 I 0.5 0.5S 0 0 good C10-41 S 0 0 I MP MP S 0 0 good C10-42 S 0 0 I FL FL S 0 0good C10-43 S 0 0 I FL FL S 0 0 good C12-22 S 0 0 D 0 Tr S 0 0 goodC12-23 S 0 0 D Tr 0.25 S 0 0 good C12-24 S 0 0 D 0.25 1 S 0 0 goodC12-27 S 0 0 I MP MP S 0 0 good C12-40 S 0 0 I >1 >1 S 0 0 good C12-45 S0 0 D 0 0 S 0 0 good C12-46 S 0 0 I FL FL S 0 0 good C16-13 S 0 0.25 — —— — — — good Mix-27 S 0 0 D 0 0 S 0 0 good C18-28 S 0 0 D Tr Tr S 0 0good Mix-31 S 0 0 D 0 Tr S 0 0 good Mix-32 S 0 0 D 0 Tr S 0 0 goodC18-33 S 0 0 D 1 1 S 0 0 good Mix-35 S 0 0 I 5 1 S 0 0 good C18-36 S 0 0D 0 Tr D 0 0 good Mix-36 S 0 0 D 0 0 S Tr Tr good C18-37 S 0 0 D 0 Tr S0 0 good Mix-37 S 0 Tr D 0 0 S Tr 0.5 good Mix-38 S Tr Tr D 0 0 S 0.50.5 good Mix-48 S 0 0 D 0 0.5 S 0 0 good PMTG-6 S 0 0 D 0 Tr S 0 0 goodPMTG-11 S 0 0 D 1 1.5 S 1 1 good MTG-11 S 0 0 D 1 1.5 S 0 0 good UTG-6 S0 Tr D 0 Tr S 0 0 good UTG-11 S 0 0 D 0.75 1 S 0 0 good UTG-13 S 0 0 D 00 S 0 0 good D = dispersable; S = soluble; I = insoluble; Tr = trace; MP= moderate precipitate; FL = flock Control result: Solubility: D; 1 h: 0mL; 24 h: Tr.Agricultural Products: Anionic Emulsifiers

Anionic surfactant samples contain a relatively high amount of water(>20%) and are prepared as oil-in-water (EW) concentrates. These aretested against controls containing a standard surfactant or a blank.Enough is formulated to test two water hardnesses (34 ppm and 1000 ppm)for each of the three samples.

Sample Preparation:

Pyraflufen (97.8% active, 0.30 g) is combined and with Stepan® C-25(methyl caprylate/caprate, 7.20 g), and N-methyl-2-pyrrolidone (1.20 g),and the mixture is stirred magnetically until dissolved. In a separatecontainer, Toximul® 8242 (castor oil ethoxylate, POE 40, product ofStepan) 0.96 g), Ninex® MT-630F (fatty acid ethoxylate, POE 30, Stepan,0.19 g), Ninex® MT-615 (fatty acid ethoxylate, POE 15, Stepan, 0.17 g),Aromatic 150 solvent (ExxonMobil, 0.37 g), and the anionic sample to betested (0.71 g) are blended. If needed, the anionic sample is melted inan oven at 50-60° C. prior to combining with the other surfactants. Whenthe pyraflufen has dissolved, the entire surfactant blend is added andmagnetically stirred until homogeneous. Deionized water (0.90 g) isslowly added with mixing to prevent gelling. Turbidity changes are notedand recorded.

Control 1 Sample:

The same procedure is followed except that the anionic sample isreplaced with Ninate® 60 L (calcium alkylbenzenesulfonate, Stepan, 0.71g).

Control 2 Sample:

No Ninate 60 L (or anionic sample) is included, and the Aromatic 150amount is increased to 1.08 g.

Emulsion Stability Testing

ASTM E1116-98 (2008) is modified as follows. Flat-bottomed, 100-mLgraduated cylinders are charged with 34 ppm or 1000 ppm water (95 mL). AMohr pipette is used to feed EW concentrate to each cylinder. Cylindersare stoppered and inverted ten times, then allowed to stand for 0.5, 1,and 24 h while recording stability at each time as type and %separation.

Spontaneity is recorded according to the following criteria: (1) poor:very thin emulsion cloud with major separation of oil droplets; (2)fair: thin emulsion cloud with minor separation of oil droplets; (3)good: thin emulsion cloud reaches the bottom of the cylinder withoutseparation of any type; (4) excellent: thick emulsion cloud reaches thebottom of the cylinder without separation of any type.

Results are provided in Table 6. The four samples indicated below arerated “good” overall as an anionic surfactant.

TABLE 6 Performance as an Anionic Emulsifier: % Separation 34 ppm water1000 ppm water Spont. 1 h 24 h Spont. 1 h 24 h Control 1 G <0.2 C   1.3C G <0.2 C  1.3 C Control 2 F 4 C 4.4 C F   4 C 4.4 C C10-19 F 3 C   3 CF 3.4 C   4 C C12-23 F 3 C 3.5 C F   3 C   3 C C18-28 F− 4 C 4.5 C F−3.4 C 3.9 C C18-33 F− 4 C 4.5 C F−   3 C 3.4 C “C” denotes separation inthe form of a cream, not a creamy oil or an oil. “Tr” denotes trace ofoil observed. “O” denotes oil separated “Spon.” = spontaneity or bloom,rated as E (excellent), G (good), F (fair), P (poor). Control 1 = nativeanionic; control 2 = no anionic emulsifier.Antimicrobial Products: Biocide Actives

Biocidal efficiency is evaluated using the rapid screen assay, anATP-based method that measures relative kill % of bacteria in a 5-min.period. The control used is first-generation ADBAC BTC 835(benzyldimethylammonium chloride). Test organisms: Pseudomonasaeruginosa and Staphylococcus aureas.

Twenty-four hour old test organism cultures are prepared in MuellerHinton broth and incubated. Samples are accurately weighed in deionizedwater or 400 ppm water to make a 1000 ppm solution taking into accountthe actives level of the sample. The 24-h culture is diluted to 10 vol.% to obtain a cell concentration of ˜10⁷ cfu/mL (colony forming unitsper mL). Reagents are prepared using the instructions provided in theBacTiter-Glo™ Microbial Cell Viability Assay kit (product of Promega)and calibrated at room temperature for 15 min. Each formulation type isdispensed (90 μL at 1000 ppm) into each row of a 96-well plate. Blankmedium, i.e., Mueller Hinton broth (10 μL) is dispensed in threereplicate wells (1-3) to determine baseline, while the organism to betested (10 μL) is dispensed in nine experimental replicate wells (4-12).The timer is started, and the test plate (baseline and experimental) isshaken for 30 s. At the end of an appropriate contact time (e.g. 5 minor 10 min), an equal amount of BacTiter-Glo reagent mix is added to eachreaction mixture, starting with the experimental samples and ending withthe baseline samples. After shaking to ensure thorough mixing, therelative luminescence units (RLUs) of each well are measured andrecorded. The % kill of 10⁷ cfu/mL after 5 min. contact time for eachorganism in DI or hard water is calculated from:% Kill=[1−(Ave. RLU of Wells_(Experimental)−Ave. RLU ofWells_(Baseline Controls))]/80000

As shown in Tables 7A and 7B, twenty of the tested compositions performas well as or better than the control when tested as antimicrobialactives.

TABLE 7A Performance as Antimicrobial Active % Kill at 5 min. contacttime, 10⁷ cfu/mL, 1000 ppm Pseudomonas aeruginosa Staphylococcus aureasOverall DI water 400 ppm DI water 400 ppm Rating control 17.9 38.9 82.870.3 C10-31 47.5 47.4 79.7 65.5 superior control 38.4 41.5 49.0 47.1C10-40 67.1 60.1 70.1 72.0 superior control 25.4 19.9 32.2 35.4 C16-1742.6 39.4 48.1 42.5 superior control 29.0 20.1 48.2 41.7 UTG-14 83.085.5 86.2 85.2 superior control 23.4 18.7 72.2 73.3 C10-18 29.6 28.975.9 71.8 good control 23.1 35.5 49.1 47.8 C12-18 58.7 40.5 42.4 66.3good control 23.1 19.7 49.1 47.8 C12-27 51.2 59.5 46.0 63.5 good control23.1 19.7 49.1 47.8 C12-41 48.9 49.0 42.0 61.9 good control 41.1 26.948.8 43.2 C12-45 59.3 25.7 43.0 35.2 good control 17.9 38.9 82.8 70.3PMTG-14 19.9 46.7 80.4 63.0 good control 17.9 38.9 82.8 70.3 PUTG-14 2150 80 63 good control 17.9 38.9 82.8 70.3 MTG-14 17.4 50.0 80.4 64.3good control = dimethylbenzylammonium chloride

TABLE 7B Performance as Antimicrobial Active % Kill at 5 min. contacttime, 10⁷ cfu/mL, 1000 ppm Pseudomonas aeruginosa Staphylococcus aureasOverall DI water 400 ppm DI water 400 ppm Rating control 38.4 26.8 61.235.7 C18-27 38.9 19.8 55.4 17.7 good Mix-27 52.4 23.2 56.1 23.2 goodMix-34 47.5 24.1 57.5 28.6 good C18-35 29.3 34.4 55.1 35.7 good Mix-3531.4 22.1 55.6 20.9 good C18-38 42.2 18.8 57.4 30.3 good C18-65 30.424.7 55.6 20.6 good Mix-65 30.5 26.1 55.3 22.1 good control =dimethylbenzylammonium chlorideHard-Surface Cleaners: Aqueous Degreasers

This test measures the ability of a cleaning product to remove a greasydirt soil from a white vinyl tile. The test is automated and uses anindustry standard Gardner Straight Line Washability Apparatus. A cameraand controlled lighting are used to take a live video of the cleaningprocess. The machine uses a sponge wetted with a known amount of testproduct. As the machine wipes the sponge across the soiled tile, thevideo records the result, from which a cleaning percentage can bedetermined. A total of 10 strokes are made using test formulationdiluted 1:32 with water, and cleaning is calculated for each of strokes1-10 to provide a profile of the cleaning efficiency of the product. Thetest sample is used as a component of different control formulationsdepending on whether it anionic, amphoteric, or nonionic.

Anionic Test Samples:

A neutral, dilutable all-purpose cleaner is prepared from propyleneglycol n-propyl ether (4.0 g), butyl carbitol (4.0 g), sodium citrate(4.0 g), Bio-Soft® EC-690 ethoxylated alcohol (1.0 g, product ofStepan), test sample (0.29 g if 100% active material), and deionizedwater (to 100.0 g solution). The control sample for anionic testingreplaces the test sample with Stepanol® WA-Extra PCK (sodium laurylsulfate, Stepan, 1.0 g, nominally 30% active material).

Nonionic and Amphoteric Test Samples:

A neutral, dilutable all-purpose cleaner is prepared from propyleneglycol n-propyl ether (4.0 g), butyl carbitol (4.0 g), sodium citrate(4.0 g), Stepanol WA-Extra PCK (sodium lauryl sulfate, 1.0 g), testsample (0.90 g if 100% active material), and deionized water (to 100.0 gsolution). The control sample for nonionic/amphoteric testing replacesthe test sample with Bio-Soft EC-690 (ethoxylated alcohol, 1.0 g,nominally 90% active material).

Soil Composition:

Tiles are soiled with a particulate medium (50 mg) and an oil medium (5drops). The particulate medium is composed of (in parts by weight)hyperhumus (39), paraffin oil (1), used motor oil (1.5), Portland cement(17.7), silica 1 (8), molacca black (1.5), iron oxide (0.3), bandy blackclay (18), stearic acid (2), and oleic acid (2). The oil medium iscomposed of kerosene (12), Stoddard solvent (12), paraffin oil (1),SAE-10 motor oil (1), Crisco (1), olive oil (3), linoleic acid (3), andsqualene (3).

Thirteen amphoteric (betaine, sulfobetaine) and five anionic (sulfonate)samples perform as well or better than the control in this test (seeTables 8 and 9). Note that quat sulfonates C10-19 and C12-19 are testedas replacements for Bio-Soft EC-690 because their net total charge iszero, although they are listed in Table 9 as “anionic” test samples.

TABLE 8 Control Runs for Gardner Straight Line Washability Test Ave. %clean after 2, 4, 6, 8, or 10 swipes 2 4 6 8 10 Control 2 47.0 57.3 61.063.7 65.2 Control 3 54.6 61.4 64.3 68.4 72.2 Control 4 52.5 58.2 59.560.9 63.3 Control 6 51.2 57.6 62.7 62.6 66.0 Control 7 52.3 56.0 61.564.3 65.0 Control 8 49.6 55.9 56.8 62.8 64.1 Control 9 55.5 61.5 66.065.9 68.4 Control 10 60.3 63.5 66.2 65.8 68.7 Control 11 53.0 61.0 63.664.6 66.2 Control 17 54.7 63.7 64.6 66.1 69.6 Control 23 60.2 64.7 66.768.3 68.7

TABLE 9 Gardner Straight-Line Washability Nonionic/Amphoteric TestSamples Ave. % clean Sample Con. # Compound class 2 4 6 8 10 RatingC12-24 3 DMAPA sulfobetaine 64.2 70.6 72.3 76.6 80.2 superior UTG-11 4DMAPA sulfobetaine 63.3 65.3 69.1 69.9 70.5 superior C10-41 6 betaine56.2 63.0 63.1 63.7 64.2 equal C10-43 23 sulfobetaine 55.5 63.2 66.066.5 67.2 equal C12-46 23 sulfobetaine 56.6 61.2 63.5 64.6 65.3 equalMix-32 11 diDMAPA dibetaine 49.6 58.1 59.4 62.1 65.5 equal C18-36 8diDMAPA monobetaine 50.2 57.3 59.9 65.5 67.8 equal Mix-36 11 diDMAPAmonobetaine 40.1 53.7 58.4 60.4 63.6 equal C18-37 8 diDMAPA betaine/AO54.2 60.1 62.4 63.9 66.6 equal PUTG-11 7 DMAPA sulfobetaine 53.9 60.562.2 66.4 67.1 equal UTG-6 11 DMAPA betaine 51.9 60.1 61.9 62.8 63.3equal MTG-6 10 DMAPA betaine 62.8 66.7 68.7 70.2 72.7 equal MTG-11 7DMAPA sulfobetaine 49.9 54.5 54.7 58.8 61.2 equal Anionic Test SamplesC10-19 2 DMAPA quat sulfonate 55.2 62.0 65.5 66.9 67.8 superior C12-23 2DMAPA betaine sulfonate 55.7 61.5 64.8 67.4 70.1 superior C12-19 9 DMAPAquat sulfonate 55.5 61.7 64.5 66.1 66.6 equal C18-28 17 DMAPA diquatsulfonate 52.2 61.1 64.3 67.6 69.2 equal C18-33 17 dibetaine sulfonate58.7 63.3 66.2 67.6 68.1 equalHard-Surface Cleaners: Foaming Glass and Window Cleaner

Control: Ammonyx® LO (lauramine oxide, 0.70 g, product of Stepan,nominally 30% active) and Bio-Terge® PAS-8S (2.00 g, sodium caprylylsulfonate, product of Stepan, nominally 38% active) are combined withisopropyl alcohol (2.50 g) and diluted to 100 mL with deionized water.

Test formulation: Test sample (0.21 g if 100% active material) andBio-Terge PAS-8S (2.00 g) are combined with isopropyl alcohol (2.50 g)and diluted to 100 mL with deionized water.

Method: The test formulation is evaluated for clarity; only clearformulations are evaluated in the low film/low streak test. The testmeasures the ability of the cleaner to leave a streak and film-freesurface on a test mirror. The test formula is applied to a mirror in acontrolled quantity and wiped with a standard substrate back and forth,leaving the spread product to dry. Once dry, the mirrors are inspectedand evaluated by a two-person panel. Ratings of “better than,” “equal”or “worse than” the control are assigned. The formulation used here isused to evaluate amphoteric and nonionic surfactants.

Eight samples, C16-13, C16-16, MTG-6, MTG-11, PMTG-6, PMTG-11, PUTG-6,and PUTG-11, perform equal to the control in the test.

Cold-Water Cleaning Performance of Compaction Laundry Detergents

This method evaluates the overall cold-water (55° F.) cleaningperformance of a laundry detergent formula comprising a concentratedblend of anionic and nonionic surfactants, a builder, C₁₆ MES, and anexperimental sample. The formulations are prepared as described below.The experimental sample is tested for its ability to improve the overallcleaning performance relative to cocamide DEA.

Preparation of Concentrated Blend:

Deionized water (90% of the required total amount) is first combined andmixed at 50° C. with Bio-Soft® S-101 (dodecylbenzene sulfonic acid, 3.27wt. %, product of Stepan). Sodium hydroxide (50% aq. solution) is addedto pH 11 (about 24% of the total amount of 4 wt. % required). Citricacid (50% aq. solution, 6.2 wt. %) is added, followed by triethanolamine(3.45 wt. %). Bio-Soft® EC-690 (laureth-7, 90% actives, 27.8 wt. %,product of Stepan) is slowly added. The pH is adjusted to the 7.8 to 8.4range, targeting 8.1 with the remaining aqueous sodium hydroxidesolution. Sodium xylene sulfonate (40% actives, 4.30 wt. %) is added,followed by a preservative and the remaining deionized water (q.s. to100 wt. %).

Preparation of an Ultra Laundry Detergent with C₁₆ MES and the Blend:

Deionized water (q.s. to 100 wt. %) is charged at 55-60° C. Theconcentrated blend prepared above (58.0 wt. %) is added whilemaintaining temperature between 50° C. and 60° C. The C₁₆ MES (87%actives, 10.34 wt. %) is slowly added and allowed to dissolve. Themixture is then allowed to cool to 35° C. The experimental sample orcocamide DEA standard (5.0 wt. %) is then added slowly and mixingcontinues until the batch is homogeneous.

Cold-Water Cleaning Evaluation:

Laundry detergent (30 g, see Part A) is charged to the laundry machine,followed by soiled/stained fabric swatches that are attached topillowcases. Wash temperature: 55° F. Rinse: 55° F. The swatches aredetached from pillowcases, dried, and ironed. Swatches are scanned tomeasure the L* a* b* values, which are used to calculate a soil removalindex (SRI) for each type of swatch. Finally, the ΔSRI is calculated,which equals the experimental sample SRI minus the SRI of apre-determined standard laundry detergent formula (or control). When|ΔSRI|≧1, differences are perceivable to the naked eye. If the value ofΔSRI is greater than or equal to 1, the sample is superior. If ΔSRI isless than or equal to −1, the sample is inferior. If ΔSRI is greaterthan −1 and less than 1, the sample is considered equal to the standard.

The following standard soiled/stained fabric swatches are used: dustsebum on cotton (DSC); beef tallow (BT); kaolin clay and wool fat onpolyester (WFK 30C), grass on cotton (GC); blueberry on cotton (BC);cocoa on cotton (EMPA 112); and blood/ink/milk on cotton (EMPA 116). Atleast three of each kind of swatch are used per wash. Swatches arestapled to pillowcases for laundering, and extra pillowcases areincluded to complete a six-pound load.

The same procedure is used to launder all of the pillowcases/swatches,with care taken to ensure that water temperature, wash time, manner ofaddition, etc. are held constant for the cold-water wash process. Whenthe cycle is complete, swatches are removed from the pillowcases, driedat low heat on a rack, and pressed briefly with a dry iron.

A Hunter LabScan® XE spectrophotometer is used to determine the L* a* b*values to calculate the SRI for every type of swatch, and the stainremoval index (SRI) is calculated as follows:

${SRI} = {100 - \sqrt{\left( {L_{clean}^{*} - L_{washed}^{*}} \right)^{2} + \left( {a_{clean}^{*} - a_{washed}^{*}} \right)^{2} + \left( {b_{clean}^{*} - b_{washed}^{*}} \right)^{2}}}$  Δ SRI = SRI_(sample) − SRI_(standard)

As shown in Table 10, two of the test samples perform as well or betterthan cocamide DEA when evaluated for cold-water cleaning performance.

TABLE 10 Performance in Cold-Water Cleaning: |ΔSRI| Values v. CocamideDEA in a C₁₆ Methyl Ester Sulfonate (MES) Formulation ΔSRI values testsample C10-41 UTG-11 dust sebum on cotton (DSC) −0.7 −0.8 beef tallow(BT) 2.4 3.7 pigment/lanolin (WFK 30C) −0.2 −1.7 grass on cotton (GC)−0.7 −1.2 blueberry on cotton (BC) 1.7 0.7 cocoa on cotton (EMPA 112)1.2 −0.3 blood/ink/milk on cotton (EMPA 116) 0.3 −0.4 overall ratingsuperior goodBooster for Bargain Laundry Detergent

This method evaluates the cleaning boosting ability of an experimentalsample when used as an additive in a bargain laundry detergentformulation that contains neutralized dodecylbenzene sulfonic acid, anon-ionic surfactant such as an ethoxylated synthetic C₁₂-C₁₅ alcohol (7EO), citric acid, monoethanolamine, triethanolamine, and a preservative.The experimental sample is tested for its ability to improve the overallcleaning performance at 1% solids level relative to Ammonyx® LO(lauramine oxide, Stepan, standard booster). Laundry detergent formula(46 g) is charged to the laundry machine, followed by soiled/stainedfabric swatches that are attached to pillowcases. Wash temperature: 90°F. Rinse: 70° F. The swatches are detached from pillowcases, dried, andironed.

The bargain laundry detergent with booster is prepared from sodiumhydroxide-neutralized dodecylbenzene sulfonic acid (NaLAS, Bio-Soft®S-101, Stepan, 33.9% actives, 41.3 wt. %), Bio-Soft® N25-7 (fattyalcohol ethoxylate, product of Stepan, 5.00 wt. %), booster (either theexperimental sample or Ammonyx LO, which is 30% actives, 3.33 wt. %,citric acid (50% aq. solution, 1.00 wt. %), monoethanolamine (1.00 wt.%), triethanolamine (1.00 wt. %), and deionized water plus preservative(balance to 100 wt. %).

The formulation is made by charging 90% of the total amount of water at50° C., then adding in order, with mixing, citric acid solution,monoethanolamine, triethanolamine, neutralized sulfonic acid, Bio-SoftN25-7, and booster. The pH is adjusted to 9.5 with 25% aq. NaOHsolution, and then preservative and the balance of the water are added.

The following standard soiled/stained fabric swatches are used: dustsebum on cotton (DSC); dust sebum on cotton/polyester (DSCP); beeftallow (BT); clay on cotton (CC); clay on cotton/polyester (CCP); grasson cotton (GC); red wine on cotton (RWC); blueberry on cotton (BC);coffee on cotton (COFC); cocoa on cotton (EMPA 112); blood/ink/milk oncotton (EMPA 116); and make-up on cotton (EMPA 143). At least three ofeach kind of swatch are used per wash. Swatches are stapled topillowcases for laundering, and extra pillowcases are included tocomplete a six-pound load.

The same procedure is used to launder all of the pillowcases/swatches,with care taken to ensure that water temperature, wash time, manner ofaddition, etc. are held constant for the cold-water wash process. Whenthe cycle is complete, swatches are removed from the pillowcases, driedat low heat on a rack, and pressed briefly with a dry iron.

A Hunter LabScan® XE spectrophotometer is used to determine the L* a* b*values to calculate the SRI for every type of swatch, and the stainremoval index (SRI) is calculated as described in the cold-watercleaning procedure discussed above.

As shown in Table 11, one test sample performs as well as the lauramineoxide control when evaluated as a booster for bargain laundrydetergents.

TABLE 11 Performance as a Booster for a Bargain Detergent Formulation:|ΔSRI| Values versus Ammonyx LO (Lauramine Oxide) ΔSRI values testsample PMTG-11 dust sebum on cotton (DSC) 0.6 dust sebum oncotton/polyester (DSCP) 0.9 beef tallow (BT) −0.7 clay on cotton (CC)−0.2 clay on cotton/polyester (CCP) −0.5 grass on cotton (GC) −0.7 redwine on cotton (RWC) −0.2 blueberry on cotton (BC) −0.9 coffee on cotton(COFC) −0.7 cocoa on cotton (EMPA 112) 0.5 blood/ink/milk on cotton(EMPA 116) 0.1 make-up on cotton (EMPA 143) 0.1 overall rating goodGas Well Foamers: Batch Dynamic Test

In this procedure, test surfactant, brine, and/or condensate are addedto a column and then agitated with nitrogen to produce foam. The wt. %of foam carried over the column after 5 min. is a measure of the testsample's performance. Results are collected as a function of brinecomposition, concentration of surfactant, and percent condensate presentin the solution.

Brines are prepared at 12.5% and 25% total dissolved solids (TDS). Thebrines are an 80:20 ratio of NaCl to CaCl₂. The density of the 12.5% TDSis 1.087 g/mL and the density of the 25% TDS is 1.184 g/mL. Brinesolutions are filtered to eliminate particulates.

Surfactant samples are tested at 5000, 2000, 1000, and 500 parts permillion of actives in each of the brine solutions listed above. A testsolution consists of brine, surfactant, and condensate when applicable.The equation below indicates how much surfactant is needed based onactives level and the density of the brine used.

${{Surfactant}\mspace{14mu}(g)} = {\frac{\left\lbrack \frac{{desired}\mspace{14mu}{ppm}}{1000} \right\rbrack}{actives} \times \frac{\left\lbrack \frac{{Total}\mspace{14mu}{Sol}^{\prime}n\mspace{14mu}(g)}{{Density}\mspace{14mu}{of}\mspace{14mu}{Brine}\mspace{14mu}\left( {g\text{/}{mL}} \right)} \right\rbrack}{1000}}$

This sample calculation shows how much of a 45% active surfactant isneeded to make a 5000 ppm solution in 12.5% TDS brine:

${\frac{\left\lbrack \frac{5000\mspace{14mu}{ppm}}{1000} \right\rbrack}{0.45\mspace{14mu}{actives}} \times \frac{\left\lbrack \frac{238.053\mspace{14mu} g}{1.087\mspace{14mu} g\text{/}{mL}} \right\rbrack}{1000}} = {2.43\mspace{14mu} g\mspace{14mu}{of}\mspace{14mu}{Surfactant}\mspace{14mu}{into}\mspace{14mu} 238.053\mspace{14mu} g\mspace{14mu}{of}\mspace{14mu} 12.5\%\mspace{14mu}{TDS}\mspace{14mu}{brine}}$

The 5000 ppm solution is used to make a 2000 ppm solution, which isdiluted to make a 1000 ppm solution, and so on. When condensate isincluded, the desired active level in the brine should be such that theactive level in the total test solution remains constant with thevarying amounts of condensate present. For example, when making a 5000ppm solution with 10% condensate, the brine/surfactant solution willactually be 5556 ppm so that the solution plus condensate will be ˜5000ppm. When testing how well a product handles condensate, either 10% or20% is added to a solution. This is done for both brine solutions atevery concentration level.

The condensate used is a low-aromatic mineral spirit, Exxsol® D-40(d=0.7636 g/mL), product of ExxonMobil. The desired amount of condensateis added to the column after the brine/surfactant solution is added.Nitrogen is fed through a glass frit in the bottom of the column and amass-flow controller is used to feed 14 standard cubic feet per hour.DataStudio (from Pasco) software and a balance are used to measure theamount of foam collected. Weight is recorded every second over thecourse of a 10-minute run. The % of liquid carried over as foam after 5min. for each brine solution at each % condensate level is reported inTable 12.

As shown in Table 12, eight of the test samples perform as well as orbetter than the control when evaluated as potential gas well foamers.

TABLE 12 Performance in Gas Well Foamers % TDS % Conc, % Carry Over at 5min. brine Condensate ppm C10-23 C10-24 C10-41 C10-43 C12-22 C12-24C12-40 UTG-11 12.5 0 500 23 — 0 7 44 54 46 36 12.5 10 500 15 15 37 32 5652 70 24 12.5 20 500 12 35 42 30 48 47 61 13 25.0 0 500 45 — 0 0 35 4452 28 25.0 10 500 22 36 49 0 31 46 31 23 25.0 20 500  9 36 46 24 15 37 37 12.5 0 1000 38 — 0 30 70 52 64 63 12.5 10 1000 34 42 48 46 67 68 74 6212.5 20 1000 36 51 61 48 51 64 66 51 25.0 0 1000 46 — 0 33 59 53 60 4025.0 10 1000 34 39 58 0 50 55 53 46 25.0 20 1000 33 33 48 43 37 42 39 2712.5 0 2000 54 — 71 56 87 74 84 70 12.5 10 2000 52 57 55 60 80 77 76 6912.5 20 2000 52 68 68 55 69 66 75 61 25.0 0 2000 54 — 52 67 72 62 82 6225.0 10 2000 54 44 69 0 58 64 60 57 25.0 20 2000 56 24 60 59 47 56 44 3912.5 0 5000 78 — 92 70 93 92 99 80 12.5 10 5000 73 91 90 85 76 82 84 6912.5 20 5000 75 93 90 76 76 76 80 60 25.0 0 5000 79 — 78 73 80 87 90 6725.0 10 5000 74 75 78 50 61 70 72 52 25.0 20 5000 64 42 72 70 53 64 6141 Rating good superior good good superior superior superior goodPersonal Care: Cleansing Application

Viscosity and mechanical shake foam tests are used to assess the likelyvalue of a particular surfactant as a secondary surfactant in cleansingapplications for personal care.

All experimental samples are evaluated for their performance versus acontrol (either cocamidopropylhydroxysultaine or cocamidopropylbetaine).

Viscosity curves are generated by preparing dilute aqueous solutions ofthe test material or control (3% active content) with 12% active sodiumlauryl ether (1) sulfate (SLES-1), then measuring viscosity by means ofa Brookfield DV-1+ viscometer. Sodium chloride is added incrementally(1-3 wt. %) and viscosity is recorded as a function of increasing NaClconcentration. A “good” result is a curve that shows a viscosity buildcomparable to the control sample. A “superior” rating indicates that thesample builds viscosity substantially more rapidly than the control.

Foaming properties are evaluated using a mechanical shake foam test.Sample solutions (calculated at 0.2% total surfactant active material)are thereafter made from aqueous solutions using 25° C. tap water. A100.0-g portion of the solution is carefully transferred to a 500-mLgraduated cylinder. Castor oil (2.0 g) is added. The cylinder isstoppered and mechanically inverted ten times, then allowed to settlefor 15 s. Foam height is recorded. After 5 min., foam height is recordedagain. The experiment is repeated without the castor oil. In one set ofexperiments, the cleansing base contains SLES-1 in both the experimentaland control runs. In a second set of experiments, the cleansing basecontains another widely used anionic surfactant, i.e., a mixture ofsodium methyl 2-sulfolaurate and disodium 2-sulfolaurate, instead ofSLES-1. A “good” result is recorded when the solution containing thetest material results in foam heights that are within +/−25 mL of thecontrol runs. Results >25 mL of the control garner a superior rating;results <25 mL of the control are rated inferior.

Ten test materials, identified in Table 13 show good overall performancein the viscosity and foam tests.

TABLE 13 Personal Care/Secondary Cleaner Viscosity and Shake Foam TestResults Viscosity Foam Viscosity Foam Sample Build Tests Sample BuildTests C10-24 good¹ good¹ PMTG-6 good³ good² C12-24 good¹ good¹ PMTG-13good² good² C12-40 good² good² PUTG-6 good² good² C16-13 good² inferior²PUTG-11 good¹ good¹ MTG-6 good³ good² MTG-14 good² good² ¹Control =cocamidopropyl hydroxysultaine; ²Control = cocamidopropyl betaine³Control = cocamide MEAPersonal Care/Antibacterial Handsoap:Method to Determine Foam Enhancement Benefit

Foam volume, which signals “clean” to consumers, is a desirableattribute in an antibacterial handsoap. Because cationic antibacterialactives are not compatible with anionic surfactants (the best foamers),achieving sufficient foam volume with them is challenging. The methodbelow identifies surfactants that provide more foam volume thancocamidopropylbetaine (actives/actives basis) in an antibacterialhandsoap base. Formulation: deionized water (q.s. to 100 wt. %),cocoglucoside (3.0 wt. %), lauramine oxide (3.0 wt. %), benzalkoniumchloride (0.1 wt. %), and test molecule or cocamidopropylbetaine (3.0wt. %).

Solutions are prepared by combining ingredients in the order prescribedabove, stirring with a stir bar or mixing gently using an overheadstirrer or manually using a spatula. Heat may be applied if the testmolecule is a solid at room temperature. Mixing is maintained to ensurea homogenous solution. The pH is adjusted to 6.5+/−0.5.

Test and control solutions are compared, with and without 2% castor oil,at 0.2% total surfactant active concentration (2.22 g solution to 100 mLwith tap water from Lake Michigan, ˜150 ppm Ca/Mg hardness) for foamvolume using the cylinder inversion test. Initial and delayed (5 min.)measurements are taken.

Rating system: Superior: a result >25 mL over the cocamidopropylbetainecontrol in both oil and no-oil systems. Good: a result within 25 mL ofthe cocamidopropylbetaine control in both oil and no-oil systems.Inferior: a result >25 mL below that of the cocamidopropylbetainecontrol in both oil and no-oil systems.

Compared with the controls, the four test materials identified in Table14 all show superior overall performance in the antibacterial handsoaptests:

TABLE 14 Superior Performance in Antibacterial Handsoap MTG-13 PMTG-13UTG-13 PUTG-13

Compared with the controls, the seventeen test materials identified inTable 15 all show good overall performance in the antibacterial handsoaptests:

TABLE 15 Good Performance in Antibacterial Handsoap C10-22 C12-41 C18-36C10-24 C16-10 Mix-65 C12-19 C18-32 MTG-6 C12-22 C18-34 UTG-6 C12-24Mix-34 UTG-14 C12-40 Mix-35Hair Conditioners: Procedure for Evaluation of Wet Combability

Hair tresses (10″ lengths, 2-3 g) are prepared using a consistent anduniform hair type (double-bleached, blond). The tresses are collectivelyshampooed with a 15% active sodium lauryl sulfate solution. Care istaken to avoid excessive tangling during shampooing. The tresses arerinsed clean with 40° C. tap water. The process is repeated to simulatea double shampoo application. The tresses are separated and tagged fortesting. A test conditioner preparation (2.0 cm³) is applied to eachclean, wet tress using a syringe. The base conditioner contains cetylalcohol (2.0%), hydroxyethyl cellulose (0.7%), cetrimonium chloride(1.0%), and water (qs to 100%). Test samples are formulated as a 2 wt. %(actives) additive to the base conditioner.

The conditioner is worked through the hair for one minute with downwardfinger strokes. The tresses are rinsed thoroughly clean under 40° C. tapwater. Excess water is squeezed from each tress to simulate towel-dryhair. The hair is combed through, at first, in the wet state. Ease ofcombing is evaluated for the test samples and the base conditioner, andqualitative ratings are assigned to the test samples in comparison tothe results with base conditioner only.

For the quaternized compositions tested, the rating system is asfollows: “superior” is an improvement of wet combing above that of theconditioner used as a control for testing; “equal” is wet combingcomparable to the conditioner used as a control for testing; and“inferior” is wet combing worse than the conditioner used as a controlfor testing.

One sample, Mix-44, is superior to the base conditioner in this test,and two samples, C16-10 and PUTG-13, perform equal to the control.

Oilfield Corrosion Inhibition: Polarization Resistance Procedure

Polarization resistance is run in dilute NACE brine (3.5 wt. % NaCl;0.111 wt. % CaCl₂.2H₂O; 0.068 wt. % MgCl₂.6H₂O) under sweet conditions(CO₂ sparged) at 50° C. The working electrode is cylindrical, made ofC1018 steel, and rotates at 3000 rpm. The counter electrode is aplatinum wire. The reference is a calomel electrode with an internalsalt bridge. A baseline corrosion rate is established over at least a3-h period. Once the baseline has been established, the corrosioninhibitor is injected and data is collected for the remainder of thetest period. The desired inhibitor concentration is 0.00011-0.0010 meq/gactive. Software details: initial delay is on at 1800 s with 0.05 mV/sstability; range: −0.02 to +0.02V; scan rate: 0.1 mV/s; sample period: 1s; data collection: ˜24 h. The final corrosion rate is an average of thelast 5-6 h of data collection. Protection rate is calculated from:

${{Protection}\mspace{14mu}{Rate}} = \frac{\begin{pmatrix}{{{Initial}\mspace{14mu}{Protection}\mspace{14mu}{{Rate}\mspace{14mu}\left\lbrack {{no}\mspace{14mu}{inhibitor}} \right\rbrack}} -} \\{{Final}\mspace{14mu}{Protection}\mspace{14mu}{{Rate}\mspace{14mu}\left\lbrack {{with}\mspace{14mu}{inhibitor}} \right\rbrack}}\end{pmatrix}*100}{{Initial}\mspace{14mu}{Protection}\mspace{14mu}{{Rate}\mspace{14mu}\left\lbrack {{no}\mspace{14mu}{inhibitor}} \right\rbrack}}$

As shown in Table 16, eight of the tested samples show overallperformance as corrosion inhibitors that equals or exceeds that of thecontrol.

TABLE 16 Performance in EOR Corrosion Inhibitors Protection Rate (%)Sample Low Dose Mid Dose High Dose Overall Rating Industry Std. A 85 8580 Control B 66 83 76 Control C 97 98 97 Control D 90 98 85 MTG-14 97 9896 superior UTG-14 97 95 95 superior C16-13 91 85 80 good Mix-36 3 57 98good PMTG-6 4 87 85 good UTG-6 98 95 92 good PUTG-6 92 92 84 goodPUTG-14 71 88 92 goodOil Field Products: Paraffin DispersantsAsphaltenes Screening Test

During acid stimulation of an oil well, a blend of HCl, HF, andcorrosion inhibitor is pumped down a well, allowed to stand, and thenpumped out. During the transfer of the acid, small amounts of ironchloride are developed in the acid solution. Once the acid blenddissolves scales and deposits in the well bore, crude oil begins to flowand mixes with the acid solution in the well. The crude oil can solidifyafter acidizing, and asphaltenes have been associated with the problem.Thus, dispersants are commonly added to the acid to prevent thesolidification.

Test Method:

A stock solution of iron-contaminated acid is made by adding 1% FeCl₃ toa 15% HCl acid solution. The sample dispersant to be tested (0.2 wt. %)is added to the acid stock solution (7.5 mL). A 15-mL vial is chargedwith the acid/dispersant mixture and crude oil (2.5 mL), and the vial isshaken vigorously for 30 s. The initial appearance is recorded. Afterstanding at room temperature for 1 h, the appearance is again noted. Thevial is placed in an oven (50° C.) for 24 h and its appearance isrecorded. The vial is allowed to cool to room temperature and appearanceis again noted. Finally, after 24 h at room temperature, appearance isagain noted. A blank sample containing crude oil and acid solution butno dispersant is run. A control sample containing soy amidoaminetrimethylammonium chloride as the dispersant is also run. Yet anothersample is run containing a 1:1 mixture of test dispersant and soyamidoamine trimethylammonium chloride.

One sample, C18-65, provides performance that is equal to the control inthis test, while C18-27 demonstrates superior performance.

Performance as a Foamer or Foam Additive for Specialty FoamerApplications

Specialty foamer applications include (among others) gypsum, concrete,and firefighting foams. The tests below evaluate foam stability when thesample is used as the primary foamer and also evaluate the sample'sperformance as an additive when used as a foam stabilizer, enhancer, ordestabilizer.

Particularly for gypsum, for which set-up times are rapid on commercialproduction lines, a desirable foam additive helps to control thecoalescence of the bubble to provide a larger bubble within a prescribedtime frame. Preferably, destabilization of the foam occurs at the end ofthe first minute in the tests below. These compositions are identifiedas “good” performers as gypsum foam destabilizers in Table 17 becausethey allow this balance to be struck effectively.

Foam Stability: Drainage Method

Surfactant solutions (0.4 wt. % active material) are prepared by mixingsurfactant with waters having varying hardnesses (342 ppm hard water or1000 ppm CaSO₄ water). Surfactant solution (100 mL) is carefullytransferred to a stainless-steel mixing cup, then mixed at high speed(27K rpm) using a Hamilton Beach mixer for 10 s. The contents arequickly poured into a 100-mL graduated cylinder to the 100-mL mark, anda stopwatch is immediately started. The amount of liquid settling in thecylinder is recorded every 15 s for 4 min. Less liquid drained indicatesgreater foam stability.

Foam Stability: Foam Half Life

A sample of surfactant solution prepared as described above (100 g) ismixed at high speed for 30 s. The mixture is quickly poured into a1000-mL graduated cylinder and a stopwatch is immediately started.Initial foam height is recorded. When 50 mL of liquid appears in thecylinder, the time and foam height are recorded as the foam half life(in seconds) and foam height at half life (in mL), respectively.

TABLE 17 Good Performance as a Foam Destabilizer for Gypsum ApplicationsC10-22 C16-10 UTG-6 C12-22 Mix-44

The preceding examples are meant only as illustrations. The followingclaims define the invention.

We claim:
 1. A quaternary ammonium, betaine, or sulfobetaine compositionderived from a fatty amidoamine, wherein the amidoamine is made byreacting a metathesis-derived C₁₀-C₁₇ monounsaturated acid,octadecene-1,18-dioic acid, or their ester derivatives and anaminoalkyl-substituted tertiary amine; wherein the quaternary ammoniumcomposition has the formula:R⁴(R³)(R²)N+(CH₂)_(n)NH(CO)R¹X⁻ wherein R¹ is —C₉H₁₆—R⁵ or—C₁₆H₃₀—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴X⁻; each of R² and R³ isindependently substituted or unsubstituted alkyl, aryl, alkenyl,oxyalkylene, or polyoxyalkylene; R⁴ is C₁-C₆ alkyl; X⁻ is a halide,bicarbonate, bisulfate, or alkyl sulfate; R⁵ is hydrogen or C₁-C₇ alkyl;and n=2 to 8; or wherein the betaine or sulfobetaine composition has theformula:R⁴(R³)(R²)N⁺(CH₂)_(n)NH(CO)R¹ wherein R¹ is —C₉H₁₆—R⁵ or—C₁₆H₃₀—(CO)NH(CH₂)_(n)N⁺(R²)(R³)R⁴; each of R² and R³ is independentlysubstituted or unsubstituted alkyl, aryl, alkenyl, oxyalkylene, orpolyoxyalkylene; R⁴ is C₂-C₄ alkylene carboxylate, C₂-C₄ alkylenesulfonate, or C₂-C₄ hydroxyalkylene sulfonate; R⁵ is hydrogen or C₁-C₇alkyl; and n=2 to 8; wherein when R⁵ is C₁-C₇ alkyl, the quaternaryammonium, betaine, or sulfobetaine composition has at least 1 mole % oftrans-Δ⁹ unsaturation.
 2. A derivative made by sulfonating orsulfitating the composition of claim
 1. 3. The composition of claim 1having at least 25 mole % of trans-Δ⁹ unsaturation.
 4. The compositionof claim 1 having at least 50 mole % of trans-Δ⁹ unsaturation.
 5. Thecomposition of claim 1 wherein the aminoalkyl-substituted tertiary amineis selected from the group consisting of N,N-dimethylaminopropylamine(DMAPA), N,N-diethylaminopropylamine, N,N-dimethylaminoethylamine, andN,N-dimethylaminobutylamine.
 6. The composition of claim 1 wherein theester derivative is a modified triglyceride made by self-metathesis of anatural oil or an unsaturated triglyceride made by cross-metathesis of anatural oil with an olefin.
 7. The composition of claim 1 wherein thenatural oil is selected from the group consisting of soybean oil, palmoil, rapeseed oil, algal oil, and mixtures thereof.
 8. The compositionof claim 1 wherein the C₁₀-C₁₇ monounsaturated acid or ester derivativecomprises a C₁₀ and a C₁₂ monounsaturated acid or ester derivative. 9.The composition of claim 1 wherein the C₁₀-C₁₇ monounsaturated acid orester derivative comprises a C₁₀ and a C₁₆ monounsaturated acid or esterderivative.
 10. A glyphosate formulation, a water-soluble herbicidecomposition, or an anionic emulsifier for agricultural compositions,each comprising the composition of claim
 1. 11. A glyphosateformulation, a water-soluble herbicide composition, or an anionicemulsifier for agricultural compositions, each comprising the derivativeof claim
 2. 12. An antimicrobial composition, a hard-surface cleaner, alaundry detergent formulation, a shampoo or hair conditioner, or apersonal cleanser or handsoap, each comprising the composition ofclaim
 1. 13. An antimicrobial composition, a hard-surface cleaner, alaundry detergent formulation, a shampoo or hair conditioner, or apersonal cleanser or handsoap, each comprising the derivative of claim2.
 14. A paraffin dispersant, a gas well foamer, or a corrosioninhibitor, each for use in oilfield applications, each comprising thecomposition of claim
 1. 15. A paraffin dispersant, a gas well foamer, ora corrosion inhibitor, each for use in oilfield applications, eachcomprising the derivative of claim
 2. 16. A foamer, foam additive, ordispersant for use in gypsum, concrete, or firefighting applicationscomprising the composition of claim
 1. 17. A foamer, foam additive, ordispersant for use in gypsum, concrete, or firefighting applicationscomprising the derivative of claim 2.